Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueos-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery

ABSTRACT

Provided are a cathode active material having a suitable particle size and high uniformity, and a nickel composite hydroxide as a precursor of the cathode active material. When obtaining nickel composite hydroxide by a crystallization reaction, nucleation is performed by controlling a nucleation aqueous solution that includes a metal compound, which includes nickel, and an ammonium ion donor so that the pH value at a standard solution temperature of 25° C. becomes 12.0 to 14.0, after which, particles are grown by controlling a particle growth aqueous solution that includes the formed nuclei so that the pH value at a standard solution temperature of 25° C. becomes 10.5 to 12.0, and so that the pH value is lower than the pH value during nucleation. The crystallization reaction is performed in a non-oxidizing atmosphere at least in a range after the processing time exceeds at least 40% of the total time of the particle growth process from the start of the particle growth process where the oxygen concentration is 1 volume % or less, and with controlling an agitation power requirement per unit volume into a range of 0.5 kW/m3 to 4 kW/m3 at least during the nucleation process.

TECHNICAL FIELD

The present invention relates to a nickel composite hydroxide, which isa precursor to a cathode active material for a nonaqueous-electrolytesecondary battery, and a manufacturing method thereof; a cathode activematerial for a secondary battery, which uses the nickel compositehydroxide as a raw material, and the manufacturing method thereof; and anonaqueous-electrolyte secondary battery that uses the cathode activematerial for a nonaqueous-electrolyte secondary battery as cathodematerial.

BACKGROUND ART

In recent years, with the spread of portable electronic equipment suchas portable telephones and notebook-sized personal computers, there is astrong need for development of a compact and lightweightnonaqueous-electrolyte secondary battery having high energy density.There is also a strong need for development of a high-output secondarybattery as the power source for driving a motor, and particularly as thebattery of the power source of transport equipment.

As a secondary battery that satisfies such a demand, there is a lithiumion secondary battery. A lithium ion secondary battery includes ananode, a cathode, an electrolyte and the like, and as the activematerial for the anode and cathode, a material capable of insertion anddesorption of lithium is used.

Currently, much research and development of various lithium ionsecondary batteries is being carried out, and among them, lithium ionsecondary batteries that use a lithium metal composite oxide withlayered structure or spinel structure for the cathode material arecapable of obtaining a 4V-class high voltage, so practical applicationof these batteries having high energy density is advancing.

Currently, as the cathode material of this kind of lithium ion secondarybattery, lithium composite oxides such as lithium cobalt composite oxide(LiCoO₂) for which synthesis is relatively easy, lithium nickelcomposite oxide (LiNiO₂) that uses nickel that is less expensive thancobalt, lithium nickel cobalt manganese composite oxide(LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂), lithium manganese composite oxide(LiMn₂O₄) that use manganese, and lithium nickel manganese compositeoxide (LiNi_(0.5)Mn_(0.5)O₂) have been proposed.

Of these cathode active materials, in recent years, much attention hasbeen placed on lithium nickel composite oxide (LiNiO₂), which has highcapacity without using cobalt of which there are only small reserves,and furthermore, lithium nickel manganese composite oxide(LiNi_(0.5)Mn_(0.5)O₂), which has excellent thermal stability. Lithiumnickel manganese composite oxide (LiNi_(0.5)Mn_(0.5)O₂) is a layeredcompound as in the case of lithium cobalt composite oxide and lithiumnickel composite oxide, and the transition metal site basically includesnickel and manganese at a composition ratio of 1:1 (refer to ChemistryLetters, Vol. 30 (2001), No. 8, p. 744).

Incidentally, as a condition for obtaining a lithium ion secondarybattery having good performance (high cycle characteristics, lowresistance, high output), the cathode material should have particleshaving a uniform and suitable particle size.

This is because when a cathode material having an excessively largeparticle size and low specific surface area is used, it is not possibleto sufficiently maintain the reaction area that reacts with theelectrolyte, and thus the reaction resistance increases and it is notpossible to obtain a battery with high output. Moreover, using a cathodematerial having a wide particle size distribution causes the voltagethat is applied to the particles inside the electrode to not be uniform,and when discharging and charging is repeatedly performed, minuteparticles are selectively deteriorated, resulting in a decrease incapacity.

In aiming for an increase in the output of a lithium ion secondarybattery, shortening the migration length of lithium ions between thecathode and anode is effective, so manufacturing a thin cathode plate isdesirable, and from this aspect as well, it is useful to use cathodematerial having a desired particle size that does not include a largeparticle size.

Therefore, in order to improve the performance of the cathode material,it is important that the lithium nickel composite oxide, which is thecathode active material, be manufactured so as to have particles havinga uniform and suitable particle size.

A lithium nickel composite oxide is normally manufactured from acomposite hydroxide, so from the aspect of making the particle size ofthe particles of lithium nickel composite oxide uniform, it is necessaryto use a composite hydroxide having uniform particle size as the rawmaterial.

In other words, from the aspect of manufacturing a high-performancelithium ion secondary battery as a final product by improving theperformance of the cathode material, it becomes necessary to use acomposite hydroxide that is composed of particles having a narrowparticle size distribution as the composite hydroxide that will becomethe raw material of the lithium nickel composite oxide of the cathodematerial.

As the nickel composite hydroxide that is used as the raw material forthe lithium nickel composite oxide, there is, for example, a compositehydroxide, of which the ratio of manganese to nickel is essentially 1:1,disclosed in JP 2004-210560 (A) in which a manganese nickel compositehydroxide is characterized by an average particle size of 5 μm to 15 μm,a tap density of 0.6 g/ml to 1.4 g/ml, a bulk density of 0.4 g/ml to 1.0g/ml, a specific surface area of 20 m²/g to 55 m²/g, a sulfate radicalcontent of 0.25% to 0.45% by weight, and in X-ray diffraction, a ratio(I₀/I₁) of the maximum intensity (I₀) of the peak at 15≤2θ≤25 and themaximum intensity (I₁) of the peak at 30≤2θ≤40 that is 1 to 6. Moreover,the surface structure and internal structure of the secondary particlesare such that the secondary particles are formed into a netlike shapethat is a collection of pleated walls formed from primary particles,with the space surrounding the pleated walls being relatively large.

Furthermore, as a manufacturing method thereof, a method is disclosed inwhich the amount of manganese ion oxidation is controlled within a fixedrange, and where in an aqueous solution having a pH value of 9 to 13 andwith the existence of a complexing agent, a mixed aqueous solution ofmanganese salt and nickel salt having an atomic ratio of manganese andnickel that is essentially 1:1 is caused to react with an alkalisolution under a suitable stirring condition, which causesco-precipitation of the resulting particles.

However, in the case of the lithium manganese nickel composite oxide andmanufacturing method thereof that are disclosed in JP 2004-210560 (A),although the structure of the particles is investigated, as can beclearly seen from the disclosed electron micrograph, coarse particlesand minute particles are mixed in the obtained particles, and thereforeuniformity of the particle size has not been investigated.

On the other hand, in regards to the particle size distribution oflithium composite oxide, JP 2008-147068 (A), for example, discloses alithium composite oxide in which the particles have an average particlesize D50, which is the particle size of a cumulative frequency of 50% inthe particle size distribution curve, of 3 μm to 15 μm, a minimumparticle size of 0.5 μm or greater and a maximum particle size of 50 μmor less, and where in the relationship among average particle size D50,average particle size D10 at a cumulative frequency of 10% and D90 at acumulative frequency of 90%, D10/D50 is 0.60 to 0.90, and D10/D90 is0.30 to 0.70. It is also disclosed that this lithium composite oxide hashigh repletion, excellent charge and discharge capacity characteristics,and does not readily degrade even under conditions of a large charge anddischarge load, so by using this lithium composite oxide, it is possibleto obtain a lithium ion nonaqueous-electrolyte secondary battery withless degradation in cycle characteristics.

However, even though the lithium composite oxide that is disclosed in JP2008-147068 (A) has an average particle size of 3 μm to 15 μm, theminimum particle size is 0.5 μm or greater and the maximum particle sizeis 50 μm or less, so minute particles and coarse particles are included.Moreover, the particle distribution is regulated by D10/D50 and D10/D90above, so it cannot be said that the particle size distribution isnarrow. In other words, the lithium composite oxide disclosed in JP2008-147068 (A) cannot be said to have particles that have sufficientlyhigh particle uniformity, and by using this lithium composite oxide, animprovement in performance of the cathode material cannot be expected,and it is difficult to obtain a lithium ion nonaqueous-electrolytesecondary battery having sufficient performance.

Furthermore, a manufacturing method for the composite hydroxide thatwill become the raw material composite oxide has also been proposed withthe objective of improving the particle size distribution. In JP2003-86182, a manufacturing method for the cathode active material for anonaqueous-electrolyte battery is proposed in which an aqueous solutionthat includes two or more kinds of transition metal salts, or an aqueoussolution and alkali solution of two or more kinds of differenttransition metal salts are simultaneously put into a reaction vessel,and by causing co-precipitation while coexisting together with areducing agent, or while passing an inert gas through the solution, ahydroxide or oxide is obtained as a precursor.

However, the technology of JP 2003-86182 classifies and collects thegenerated crystals, so in order to obtain a product having a uniformparticle size, strict management of the manufacturing conditions isconsidered to be necessary, and thus production on an industrial scaleis difficult. Moreover, uniformity of particle size is achieved throughclassification, so the degree of uniformity will not exceed theclassification precision.

Furthermore, in order to increase the output of a battery, increasingthe reaction surface area without changing the particle size iseffective. In other words, by making the particles porous or making theparticle structure hollow, it is possible to increase the surface areathat contributes to the battery reaction, and thus it becomes possibleto reduce the reaction resistance.

For example, in JP 2004-253174, a cathode active material for anonaqueous-electrolyte secondary battery that has at least a layeredlithium transition metal composite oxide, where the lithium transitionmetal composite oxide is composed of hollow particles having anouter-shell section on the outside and a space on the inside of theouter-shell section. It is also disclosed that this cathode activematerial for a nonaqueous-electrolyte secondary battery has excellentbattery characteristics such as cycle characteristics, outputcharacteristics, thermal stability characteristics and the like, and canbe suitably used in a lithium ion secondary battery.

The cathode active material that is disclosed in JP 2004-253174 (A) hashollow particles, so the increase in specific surface area is expectedcompared to solid particles, however, it makes no mention of particlesize thereof. Therefore, an improvement in reactivity with theelectrolyte due to the increase in specific surface area can beexpected, however, the effect on the migration length of lithium ionsdue to making the particles minute is unclear, and sufficientimprovement of the output characteristic cannot be expected.Furthermore, in regards to the particle size distribution, thedistribution is considered to be the same as that of conventionalcathode active material, so there is a high probability that selectivedegradation of minute particles due to lack of uniformity of the appliedvoltage inside the electrodes will occur, and that the battery capacitywill drop.

As described above, at the current time neither a lithium compositeoxide that sufficiently improves the performance of a lithium ionsecondary battery nor a composite oxide that is the raw material forthat composite oxide have been developed. Moreover, various methods formanufacturing a composite hydroxide have been investigated, however, onan industrial scale, a method capable of manufacturing a compositehydroxide that will become the raw material of a composite oxide that isable to sufficiently improve the performance of a lithium ion secondarybattery has not been developed. In other words, development of a cathodeactive material having a suitable particle size, and particularly,having good particle size uniformity and suitable a particle size ofabout 8 μm to 16 μm, and furthermore, a cathode active material having alarge reaction surface area, for example, having hollow structure, hasnot been performed, and there is a need for development of such acathode active material and industrial manufacturing method thereof.

RELATED ART LITERATURE Patent Literature

-   [Patent Literature 1] JP 2004-210560 (A)-   [Patent Literature 2] JP 2008-147068 (A)-   [Patent Literature 3] JP 2003-86182 (A)-   [Patent Literature 4] JP 2004-253174 (A)

Non-Patent Literature

[Non-patent Literature 1] Chemistry Letters, Vol. 30 (2001), No. 8, p.744

SUMMARY OF INVENTION Problems to be Solved by Invention

An object of the present invention is to provide: a cathode activematerial for a nonaqueous-electrolyte secondary battery, the particledistribution thereof having good uniformity and good repletion, and whenused in a battery is capable of lowering the cathode resistance value; anonaqueous-electrolyte secondary battery having excellent batterycharacteristics that uses the cathode active material; and a nickelcomposite hydroxide having a suitable particle size and highly uniformparticle size, that as a precursor to the cathode active material, makesit possible to manufacture such a cathode active material.

Moreover, another object of the present invention is to provide: acathode active material that is this kind of cathode active material andthat, by having a hollow structure, has a higher specific surface area;and a nickel composite hydroxide that, as a precursor to a cathodeactive material, makes it possible to manufacture such a cathode activematerial.

Furthermore, another object of the present invention is to provide amethod for industrially manufacturing this kind of nickel compositematerial and cathode active material having these kinds of excellentcharacteristics.

Means for Solving Problems

The inventors learned as a result of diligent investigation of a lithiumnickel composite oxide that is capable of displaying excellent batterycharacteristics when used as the cathode active material of a lithiumion secondary battery, a lithium nickel composite oxide having highlyuniform particle size can be obtained by controlling the particle sizedistribution of a nickel composite hydroxide, which is the raw material,and making the particle size uniform.

Moreover, the inventors learned that when the structure of the nickelcomposite hydroxide has a center section that is composed of minuteprimary particles, and an outer-shell section on the outside of thecenter section that is composed of primary particles that are largerthan the minute primary particles, a lithium composite oxide having ahollow structure can be obtained.

Furthermore, the inventors learned that the nickel composite hydroxidecan be obtained by separating a nucleation process and a particle growthprocess by controlling the pH during crystallization, and by controllingthe agitation power requirement for the reaction solution.

The present invention was achieved based on this technical knowledge. Inother words, the manufacturing method for manufacturing nickel compositehydroxide that is a precursor to a cathode active material for anonaqueous-electrolyte secondary battery of the present invention is amethod that forms a nickel composite hydroxide by a crystallizationreaction that is expressed by the general expression:

Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a) (x+y+z+t=1, 0.3≤x, 0≤y≤0.55, 0≤z≤0.4,0≤t≤0.1, 0≤a≤0.5, and M is one or more of additional element that isselected from among Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W), including:

a nucleation process that performs nucleation by controlling anucleation aqueous solution that includes a metal compound that containsat least nickel and an ammonium ion donor so that the pH value at astandard solution temperature of 25° C. becomes 12.0 to 14.0; and

a particle growth process causes nuclei to grow by controlling aparticle growth aqueous solution that contains nuclei that were formedin the nucleation process so that the pH value at a standard solutiontemperature of 25° C. becomes 10.5 to 12.0, and so that the pH value islower than the pH value during the nucleation process;

the crystallization process being performed in a non-oxidizingatmosphere at least in a range after the processing time exceeds 40% ofthe total time of the particle growth process from the start of theparticle growth process where the oxygen concentration is 1 volume % orless, and with controlling an agitation power requirement per unitvolume into a range of 0.5 kW/m³ to 4 kW/m³ at least during nucleationprocess.

More specifically, when obtaining a cathode active material that iscomposed of dense secondary particles, controlling the atmosphere in thenucleation process and in the particle growth process, thecrystallization reaction is performed over both processes in anon-oxidizing atmosphere where the oxygen concentration is 1 volume % orless.

On the other hand, when obtaining a cathode active material that iscomposed of secondary particles having a hollow structure, nucleation isperformed in the nucleation process in an oxidizing atmosphere in whichthe oxygen concentration is greater than 1 volume %, after which theatmosphere is switched from an oxidizing atmosphere to a non-oxidizingatmosphere in which the oxygen concentration is 1 volume % or less in arange of from 0% to 40% of the total time of the particle growth processfrom the start of the particle growth process, and the crystallizationreaction continues to be performed.

In this case, when obtaining a cathode active material that is composedof secondary particles having a hollow structure, the nickel content andthe manganese content of the nickel composite hydroxide are regulated inthe general expression above so as to be 0.3≤x≤0.7 and 0.1≤y≤0.55,respectively.

Preferably, the non-oxidizing atmosphere is an inert gas atmosphere, andthe oxygen concentration in the oxidizing atmosphere is 10 volume % orgreater.

Preferably, the particle growth aqueous solution is formed by adjustingthe pH value of the nucleation aqueous solution after the nucleationprocess has finished, or preferably, the particle growth aqueoussolution is formed by adding a solution that includes nuclei that wereformed in the nucleation process to an aqueous solution that isdifferent than the nucleation aqueous solution in which nuclei wereformed.

Preferably, in the particle growth process, part of the liquid of theparticle growth aqueous solution is removed.

Preferably, the ammonium ion concentration of the aqueous solutions inthe nucleation process and particle growth process is kept within therange of 3 g/L to 25 g/L.

Preferably, the nickel composite hydroxide that was obtained in theparticle growth process is covered by a compound that includes one ormore kind of the additional elements.

The nickel composite hydroxide is a precursor to a cathode activematerial for a nonaqueous-electrolyte secondary battery of the presentinvention is expressed by the general expression:

Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a) (x+y+z+t=1, 0.3≤x, 0≤y≤0.55, 0≤z≤0.4,0≤t≤0.1, 0≤a≤0.5, and M is one or more of additional element that isselected from among Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W), and isnearly spherical secondary particles that are formed by pluralneedle-like or plate-like primary particles clumping together; thesecondary particles having an average particle size of greater than 7 μmand less than or equal to 15 μm, and a value [(d90−d10)/average particlesize], which is an index that indicates the extent of the particle sizedistribution, of 0.55 or less.

In the case where the precursor of the cathode active material has adense structure, preferably, the average particle size of the primaryparticles of the secondary particles is in the range 0.3 μm to 3 μm.

On the other hand, in the case where the precursor of the cathode activematerial has a hollow structure, the nickel content and the manganesecontent of the nickel composite hydroxide in the general expressionabove are 0.3≤x≤0.7, and 1≤y≤0.55, respectively; and the nickelcomposite hydroxide is composed of secondary particles that are nearlyspherical secondary particles that are formed by plural primaryparticles clumping together, and have a center section composed ofminute primary particles, and an outer-shell section on the outside ofthe center section, that is composed of primary particles that arelarger than the minute primary particles.

Preferably, the minute primary particles have an average particle sizeof 0.01 μm to 0.3 μm, and the primary particles that are larger than theminute primary particles have an average particle size of 0.3 μm to 3μm.

Preferably, one kind or more of the additional elements above isuniformly distributed inside the secondary particles and/or uniformlycoated on the surface of the secondary particles.

The manufacturing method for a cathode active material for anonaqueous-electrolyte secondary battery of the present invention iscomposed of a lithium nickel composite oxide that is expressed by thegeneral expression:

L_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (−0.05≤u≤0.50, x+y+z+t=1, 0.3≤x,0≤y≤0.55, 0≤z≤0.4, 0≤t≤0.1, and M is one or more kind of additionalelement that is selected from among Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Taand W), and has a hexagonal crystal structure with a layered structure;and includes:

a mixing process wherein the nickel composite hydroxide is mixed with alithium compound to form a lithium mixture; and

a calcination process that calcines the lithium mixture that was formedin the mixing process in an oxidizing atmosphere at 650° C. to 1000° C.

Preferably, there is further a heat treatment process before the mixingprocess that heats the nickel composite hydroxide at a temperature of105° C. to 750° C.

Preferably, the lithium mixture is adjusted so that the ratio of the sumof the atoms of metals other than lithium that are included in thelithium mixture and the number of atoms of lithium is 1:0.95 to 1.5.

Preferably, the lithium compound is lithium hydroxide, lithiumcarbonate, or a mixture of these.

Preferably, during the calcination process, pre-calcination is performedbeforehand at a temperature of 350° C. to 800° C.

The cathode active material for a nonaqueous-electrolyte secondarybattery of the present invention is composed of a lithium nickelcomposite oxide that is expressed by the general expression:

L_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂ (−0.05≤u≤0.50, x+y+z+t=1, 0.3≤x,0≤y≤0.55, 0≤z≤0.4, 0≤t≤0.1, and M is one or more kind of additionalelement that is selected from among Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Taand W), and has a hexagonal crystal structure with a layered structure;the cathode active material having the average particle size of greaterthan 8 μm and less than or equal to 16 μm, and a value[(d90−d10)/average particle size], which is an index that indicates theextent of the particle size distribution, of 0.60 or less. This cathodeactive material is composed of dense secondary particles or secondaryparticles having a hollow structure. In the case of a hollow structure,preferably, the nickel content and the manganese content of the lithiumnickel composite oxide in the general expression above is 0.3≤x≤0.7 and0.1≤y≤0.55, respectively. The secondary particles of the cathode activematerial having this hollow structure have an outer-shell section inwhich primary particles that are clumping together are sintered, and ahollow section that exists inside the outer-shell section.

Preferably, the ratio of the thickness of the outer-shell section withrespect to the particle size of the lithium nickel composite oxide is 5%to 45%.

In the case of dense secondary particles, preferably, the tap density ofthe cathode active material for a nonaqueous-electrolyte secondarybattery is 1.8 g/cm³ or more.

The nonaqueous-electrolyte secondary battery of the present invention issuch that the cathode is formed using the cathode active material for anonaqueous-electrolyte secondary battery of the present inventiondescribed above.

Advantageous Effect of Invention

With the present invention, it is possible to obtain a nickel compositehydroxide having a suitable particle size and highly uniform particlesize. By using such a nickel composite hydroxide as raw material, it ispossible to obtain a cathode active material composed of a lithiumnickel composite oxide that has a suitable particle size and highlyuniform particle size.

Furthermore, in this kind of nickel composite hydroxide, it is possibleto make the characteristics of the primary particles of the secondaryparticles different on the outside and the inside. By using a nickelcomposite hydroxide having such a structure as raw material, it ispossible to obtain a lithium nickel composite oxide having a hollowstructure and high specific surface area.

When a cathode active material that is composed of this kind of lithiumnickel composite oxide is used in a nonaqueous secondary battery, highcapacity and high output of the battery is possible, and a nonaqueoussecondary battery that is made using a cathode that includes thiscathode active material has excellent battery characteristics.

Moreover, the manufacturing methods for a nickel composite hydroxide andcathode active material that are provided by the present invention aresimple and suitable for large-scale production, and thus have a verylarge industrial value.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a general flowchart of a process for manufacturing the nickelcomposite hydroxide of the present invention.

FIG. 2 is a general flowchart of another process for manufacturing thenickel composite hydroxide of the present invention.

FIG. 3 is a general flowchart of a process for manufacturing a lithiumnickel composite oxide, which is an active cathode material, from thenickel composite hydroxide of the present invention.

FIG. 4 is a flowchart from manufacturing the nickel composite hydroxideof the present invention to manufacturing a nonaqueous-electrolytesecondary battery.

FIG. 5 is an FE-SEM photograph (5000× magnification rate) thatillustrates an example of the nickel composite hydroxide of the presentinvention.

FIG. 6 is an FE-SEM photograph (5000× magnification rate) thatillustrates the cross section of an example of secondary particles ofthe nickel composite hydroxide of the present invention.

FIG. 7 is an FE-SEM photograph (5000× magnification rate) thatillustrates an example of the lithium nickel composite oxide, which isthe cathode active material of the present invention.

FIG. 8 is an FE-SEM photograph (5000× magnification rate) thatillustrates the cross section of an example of the lithium nickelcomposite oxide, which is the cathode active material of the presentinvention.

FIG. 9 is an FE-SEM photograph (5000× magnification rate) thatillustrates another example of the lithium nickel composite oxide, whichis the cathode active material of the present invention.

FIG. 10 is an FE-SEM photograph (5000× magnification rate) thatillustrates the cross section of another example of the lithium nickelcomposite oxide, which is the cathode active material of the presentinvention.

FIG. 11 is an FE-SEM photograph (5000× magnification rate) thatillustrates another example of the lithium nickel composite oxide, whichis the cathode active material of the present invention.

FIG. 12 is an FE-SEM photograph (5000× magnification rate) thatillustrates the cross section of another example of the lithium nickelcomposite oxide, which is the cathode active material of the presentinvention.

FIG. 13 illustrates an equivalent circuit that is used in a measurementexample and analysis of impedance evaluation.

FIG. 14 is a cross-sectional view illustrating a coin battery that isused in battery evaluation.

MODES FOR CARRYING OUT INVENTION

The present invention relates to: (1) a nickel composite hydroxide thatis a precursor to a cathode active material for a nonaqueous-electrolytesecondary battery and the manufacturing method thereof; (2) anonaqueous-electrolyte secondary battery that uses the nickel compositehydroxide and the manufacturing method thereof; and (3) anonaqueous-electrolyte secondary battery that uses that cathode activematerial for a nonaqueous-electrolyte secondary battery for the cathode.

The effect of the cathode active material for a nonaqueous-electrolytesecondary battery that is used for a cathode is large for improving theperformance of a nonaqueous-electrolyte secondary battery. In order toobtain a cathode active material for a nonaqueous-electrolyte secondarybattery that is capable of obtaining excellent battery characteristics,the particle size, particle size distribution, and the specific surfacearea are important factors, and a cathode active material that has adesired particle structure and is adjusted to a desired particle sizeand particle size distribution is preferred. In order to obtain thatkind of cathode active material, it is necessary to use a nickelcomposite hydroxide as a precursor that is composed of secondaryparticles that have desired particle structure and desired particle sizeand particle size distribution.

In the following, the inventions of (1) to (3) above will be explainedin detail, however, first, the nickel composite hydroxide and themanufacturing method thereof, which are a large feature of the presentinvention, will be explained.

1.1. Nickel Composite Hydroxide

(Composition)

The nickel composite hydroxide of the present invention is adjusted sothat the composition is as expressed by the following generalexpression. By manufacturing a lithium nickel composite oxide using anickel composite hydroxide having this kind of composition as aprecursor, when an electrode, which has this lithium nickel compositeoxide as a cathode active material, is used in a battery, it is possibleto reduce the value of the measured cathode resistance, and improve thebattery performance.Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a)  General Expression:

(x+y+z+t=1, 0.3≤x, 0≤y≤0.55, 0≤z≤0.4, 0≤t≤0.1, 0≤a≤0.5, and M is one ormore kind of additional element that is selected from among Al, Ti, V,Cr, Zr, Nb, Mo, Hf, Ta and W)

In the present invention, when trying to obtain a cathode activematerial having hollow structure, the amount of nickel and the amount ofmanganese that is included in the nickel composite hydroxide that is theprecursor of that cathode active material is adjusted so as to be0.3≤x≤0.7 and 0.1≤y≤0.55, respectively, in the general expression givenabove, and by setting the amount of manganese included to a high amount,it is possible to make a nickel composite hydroxide having secondaryparticles that make it easy to obtain a hollow structure.

When a cathode active material is obtained using a composite hydroxideas raw material, the composition ratio of this composite hydroxide(Ni:Mn:Co:M) is maintained even in the obtained cathode active material.Therefore, the composition ratio of the composite hydroxide of thepresent invention is adjusted to become the same composition ratio thatis required in the cathode active material to be obtained.

(Average Particle Size)

The average particle size of the nickel composite hydroxide of thepresent invention is adjusted within a range of greater than 7 μm andequal to or less than 15 μm, and preferably greater than 7 μm and equalto or less than 11 μm. By controlling the average particle size of thenickel composite hydroxide within such a range, it is possible to adjustthe cathode active material that is obtained using this compositehydroxide as a raw material to a specified average particle size(greater than 8 μm and equal to or less than 16 μm). In this way, theparticle size of the composite hydroxide is correlated with the particlesize of the cathode active material to be obtained, so that particlesize affects the characteristics of a battery that uses the cathodeactive material as the cathode material.

When the average particle size of this composite hydroxide is equal toor less than 7 μm, the average particle size of the cathode activematerial that is obtained also becomes small, and thus the fillingdensity of the cathode decreases, and the battery capacity per volumedecreases. When the average particle size of the composite hydroxide isgreater than 15 μm, the specific surface area of the cathode activematerial to be obtained decreases, and therefore with reducing theinterface with the electrolyte, the resistance of the cathode increasesand the output characteristic of the battery decreases.

(Particle Size Distribution)

The composite hydroxide of the present invention is adjusted so that avalue [(d90−d10)/average particle size] that is an index indicating theexpanse of the particle size distribution is equal to or less than 0.55,and preferably equal to or less than 0.52.

The particle size distribution of the cathode active material isstrongly affected by the composite hydroxide that is the raw material,and for example, when minute particles or coarse particles are mixed inthe composite hydroxide, there will similarly be minute particles orcoarse particles that exist in the cathode active material. In otherwords, when the index [(d90−d10)/average particle size] is greater than0.55 and the particle size distribution is large, there are also minuteparticles or coarse particles that exist in the cathode active material.

When a cathode is formed by using a cathode active material in whichthere are many minute particles, there is a possibility that heat willbe generated due to a local reaction of the minute particles, and thussafety of the battery decreases, and the minute particles selectivelydegrade, so cycle characteristics of the battery become bad. On theother hand, when a cathode is formed using a cathode active material inwhich there are many large particles, it is not possible to obtainsufficient reaction surface area between the electrolyte and the cathodeactive material, and thus the battery output drops due to an increase inreaction resistance.

Therefore, in the composite hydroxide of the present invention, byadjusting the particle size distribution so that the index[(d90−d10)/average particle size] is equal to or less than 0.55, therange of the particle size distribution of the cathode active materialthat uses this composite hydroxide as a precursor also becomes narrow,and it is possible make the particle size uniform. In other words, forthe particle size distribution of the cathode active material, it ispossible to make the index [(d90−d10)/average particle size] equal to orless than 0.60. As a result, in a battery that uses a cathode activematerial, which is formed using the composite hydroxide of the presentinvention as a precursor, as the cathode material, it is possible toachieve good output characteristics and high output.

Here, it is also feasible to obtain a composite hydroxide having anarrow particle size distribution by classification of a compositehydroxide having a large particle size distribution, however, sieveclassification has bad precision, and even when an apparatus such as awet cyclone is used, it is not possible to perform classification into asufficiently narrow particle size distribution. Therefore, in this kindof industrial classification method, it is difficult to obtain acomposite hydroxide having a uniform particle size and a narrow particlesize distribution such as that of the composite hydroxide of the presentinvention.

In the index [(d90−d10)/average particle size] indicating the expanse ofthe particle size distribution, d10 is the particle size when the numberof particles of each particle size is accumulated from the side having asmall particle size, and that accumulated volume is 10% of the totalvolume of all particles. Moreover, d90 is the particle size when thenumber of particles of is similarly accumulated, and that accumulatedvolume is 90% of the total volume of all particles.

The method for finding the average particle, d10 and d90 is notparticularly limited, however, for example, can be found from theintegrated volume value that is measured using a laser diffraction andscattering type particle size analyzer. As the average particle size, itis possible to use d50 that is the particle size that accumulated valueis 50% of the total volume of all particles as with d90.

(Particle Structure)

The nickel composite hydroxide of the present invention is composed ofspherical secondary particles that are formed by clumping together ofplural primary particles. The shape of the primary particles thatconstitute the secondary particles can be various shapes such as plateshaped, needle shaped, cuboid shaped, elliptical shaped, rhombus shapedand the like. With regard to the aggregation state of the primaryparticles, as well as the state where the primary particles clumptogether in a random direction, the state where the primary particlesclump together such that the major axis direction of the primaryparticles is aligned with the radiation direction from the center of thesecondary particles can be applied to the present invention.

However, in the present invention, preferably plate shaped and/or needleshaped primary particles clump together in a random direction to formsecondary particles. This is because in the case of this kind ofstructure, nearly uniform spacing occurs between primary particles, andwhen mixed with a lithium compound and calcined, the melted lithiumcompound goes inside the secondary particles, and diffusion of lithiumis sufficiently performed.

In the present invention, the average particle size of primary particlesthat constitute the secondary particles is preferably adjusted withinthe range of 0.3 μm to 3.0 μm. By adjusting the size of the primaryparticles in this way, suitable spacing between the primary particles isobtained, and during calcination, sufficient dispersion of lithium intothe secondary particles can be easily performed. The average particlesize of the primary particles is even more preferably 0.4 μm to 1.5 μm.

When the average particle size of the primary particles is less than 0.3μm, the sintering temperature during calcination becomes lower, thesintering between secondary particles is increased, and coarse particlesare included in the cathode active material that is obtained. On theother hand, when the average particle size is greater than 0.3 μm, inorder for the crystallinity of the cathode active material that isobtained to be sufficient, it is necessary to make the calcinationtemperature high, and by performing calcination at this kind of hightemperature, sintering occurs between secondary particles, and thecathode active material shifts from having a suitable particle sizedistribution.

The feature of the present invention is that by regulating the averageparticle size, the particle size distribution, and the particlestructure of the secondary particles of the nickel composite hydroxideas described above, it is possible to manufacture a cathode activematerial that has suitable particle size and high uniformity of particlesize. In the present invention, as the structure of the secondaryparticles of the cathode active material, it is possible to use a solidstructure that is dense from the outside to the inside, and it is alsopossible to use a hollow structure that is dense only on the outside andthat is hollow on the inside. As the precursor of a cathode activematerial having dense structure, it is similarly possible to use nickelhydroxide particles having a dense structure. On the other hand, as theprecursor of a cathode active material having hollow structure, it ispossible to use a nickel composite hydroxide that has a structure wherethe characteristics of the clumped primary particles are different onthe outside and inside.

In other words, the particle structure of the nickel composite hydroxidethat is a precursor of a cathode active material having a hollowstructure has a center section that is composed of minute primaryparticles, and an outer-shell section on the outside of the centersection that is composed of primary particles that are larger than theminute particles.

In this nickel composite hydroxide, the center section has a structurein which the minute primary particles are arranged so as to abut eachother and there are many gaps therebetween, and the outer-shell sectionhas a sense structure composed of large and thick plate shaped primaryparticles. Therefore, during calcination, sintering proceeds at a lowertemperature in the center section than in the outer-shell section, andthe primary particles of the center section shrink going from the centerof the secondary particles toward the outer-shell side where sinteringis slow. Moreover, the center section has a low density, so the amountof shrinking is large, and thus the center section becomes asufficiently large hollow space.

Even in the case of obtaining this kind of hollow structure, thecharacteristics of the primary particles have an effect on the formationthereof. In other words, preferably in the center section the minuteprimary particles clump together in a random direction, and in theouter-shell section, larger primary particles clump together in a randomdirection. As a result of this kind of clumping in a random direction,the shrinkage in the center section occurs equally, and it is possibleto form a sufficiently large space in the cathode active material.

Moreover, in this case, the average particle size of the minute primaryparticles is preferably 0.01 μm to 0.3 μm, and even more preferably 0.1μm to 0.3 μm. When the average particle size of the minute primaryparticles is less than 0.01 μm, a sufficiently large center section maynot be formed in the composite hydroxide, and when the average particlesize is greater than 0.3 μm, the low temperature at the start ofsintering and shrinkage are not sufficient, so it may not be possible toobtain a sufficiently large space after calcination. The characteristicsof the primary particles of the outer-shell section should be the sameas described above.

For secondary particles having this kind of double structure, thethickness of the outer-shell section is such that preferably the ratiowith respect to the particle size of the secondary particles is 5% to45%, and more preferably 7% to 35%. Secondary particles of cathodeactive material that is obtained with this kind of composite hydroxideas a raw material have a hollow structure, and the ratio of thethickness of the outer-shell section with respect to the particle sizeof the secondary particles is such that the ratio of secondary particlesof composite hydroxide above is mostly maintained. Therefore, by makingthe ratio of the thickness of the outer-shell section with respect tothe particle size of secondary particles within the range describedabove, it is possible to form a sufficient hollow section in the lithiumnickel composite oxide. When the thickness of the outer-shell section istoo thin and the ratio with respect to the particle size of thesecondary particles is less than 5%, in the calcination process whenmanufacturing cathode active material, shrinkage of the compositehydroxide becomes large, and sintering occurs between the secondaryparticles of the lithium nickel composite oxide, and thus the particlesize distribution of the cathode active material may become bad. On theother hand, when the ratio is greater than 45%, a problem may occur inthat a sufficiently large center section cannot be formed.

The particle size of the minute primary particles in the center section,the particle size of the larger primary particles in the outer-shellsection, and the ratio of the thickness of the outer-shell section withrespect to the particle size of the secondary particles can be measuredby observation of the cross section of the nickel composite hydroxideusing a scanning electron microscope.

For example, plural secondary particles of nickel composite hydroxidesare embedded in resin or the like, and a state in which the crosssection of the particles can be observed is created by performing crosssection polishing. The particle size of minute primary particles in thecenter section and the particle size of primary particles in theouter-shell section can be found by measuring the maximum diameters ofthe cross section of preferably 10 or more of the primary particlesamong the secondary particles as the particle size, and calculating theaverage value.

Moreover, the ratio of the thickness of the outer-shell section withrespect to the particle size of secondary particles can be found asdescribed below. Particles of which the cross section in nearly thecenter thereof can be observed are selected from the secondary particlesin the resin described above, and at three or more arbitrary locations,the distance between two points that is the shortest distance betweenthe outer circumference of the outer-shell section and the innercircumference of the center section side thereof is measured to find theaverage thickness of the outer-shell section for each particle. Then bydividing the above average thickness of the outer-shell section by thedistance between two arbitrary points on the outer circumference of thesecondary particle where the distance has a maximum value, the ratio ofthe thickness of the outer-shell section with respect to each particleis found. Furthermore, by taking the average of the ratios with respectto each particle that was found for 10 or more particles, it is possibleto find the ratio of the thickness of the outer-shell section withrespect to the particle size of secondary particles in the nickelcomposite hydroxide above.

1.2. Method for Manufacturing Nickel Composite Hydroxide

The method for manufacturing the nickel composite hydroxide of thepresent invention relates to a method for manufacturing nickel compositehydroxide by a crystallization reaction in which there is a) anucleation process for performing nucleation, and b) a particle growthprocess for causing the nuclei that were generated in the nucleationprocess to grow.

In other words, in a conventional continuous crystallization method, thenucleation reaction and the particle growth reaction proceedsimultaneously in the same tank, so the particle size distribution ofthe composite hydroxide obtained covers a large range. On the otherhand, the method for manufacturing composite hydroxide of the presentinvention is characterized in that the time during which mainly thenucleation process occurs (nucleation process), and the time duringwhich mainly the particle growth reaction occurs (particle growthprocess) are clearly separated, and by controlling the agitation powerrequirement per unit volume of reaction solution into a range of 0.5kW/m³ to 4 kW/m³ at least during the nucleation process, the averageparticle size of the composite hydroxide that is obtained is controlledso as to be within a range that is greater than 7 μm and equal to orless than 15 μm, and the narrow particle distribution is achieved.

First, the outline of the method for manufacturing the compositehydroxide of the present invention will be explained based on FIG. 1 andFIG. 2. In FIG. 1 and FIG. 2, Section (A) corresponds to the nucleationprocess, and Section (B) corresponds to the particle growth processrespectively.

(Nucleation Process)

As illustrated in FIG. 1, in the method for manufacturing compositehydroxide of the present invention, first, plural metal compounds thatinclude at least nickel are dissolved in water at specified ratios tomake a mixed aqueous solution. In the method for manufacturing compositehydroxide of the present invention, the composition ratios of each ofthe metals in the composite hydroxide that is obtained will be the sameas the composition ratios of each of the metals in the mixed aqueoussolution.

Therefore, the mixed aqueous solution is made by adjusting the ratios ofthe metal compounds that are dissolved in water so that the compositionratios of each of the metals in the mixed aqueous solution are the samecomposition ratios of each metal in the nickel composite hydroxide ofthe present invention.

On the other hand, an alkali aqueous solution such as sodium hydroxideaqueous solution, an ammonia aqueous solution that includes an ammoniumion donor, and water are mixed in a reaction tank to form an aqueoussolution. By adjusting the amount of alkali aqueous solution that issupplied, the pH value of this aqueous solution (hereafter, referred toas the “pre-reaction aqueous solution”) is adjusted so that at astandard solution temperature of 25° C. the value is within a range of12.0 to 14.0, and preferably 12.3 to 13.5. Moreover, by adjusting theamount of ammonium aqueous solution that is supplied, the density of theammonium ions inside the pre-reaction aqueous solution is adjusted so asto preferably be 3 g/L to 25 g/L, and more preferably to be 5 g/L to 20g/L, and even more preferably be 5 g/L to 15 g/L. The temperature of thepre-reaction aqueous solution is also adjusted so as to preferably be20° C. to 60° C., and to more preferably to be 35° C. to 60° C. The pHvalue and the ammonium ion density of the aqueous solution in thereaction tank can be measured using a typical pH meter and ion meter.

After the temperature and pH of the pre-reaction aqueous solution in thereaction tank have been adjusted, the mixed aqueous solution is suppliedto the reaction tank while agitating the pre-reaction aqueous solution.As a result, the pre-reaction aqueous solution and the mixed aqueoussolution are mixed inside the reaction tank, a nucleation aqueoussolution, which is the reaction aqueous solution in the nucleationprocess, is formed, and minute nuclei of the composite hydroxide aregenerated in the nucleation aqueous solution. When this occurs, the pHvalue of the nucleation aqueous solution is within the range describedabove, so the generated nuclei hardly grow, and generation of nucleipreferentially occurs.

While nuclei are generated by supplying mixed aqueous solution, the pHvalue of the nucleation solution and the ammonium ion density changes,so together with the mixed aqueous solution, alkali solution and ammoniaaqueous solution are supplied in order to perform control so that the pHvalue of the nucleation solution at a standard solution temperature of25° C. is in the range 12.0 to 14.0, and so that ammonium ion density isin the range 3 g/L to 25 g/L.

By supplying mixed aqueous solution, alkali aqueous solution and ammoniaaqueous solution to the nucleation aqueous solution, continuousgeneration of new nuclei is maintained. After a specified amount ofnuclei have been generated in the nucleation aqueous solution, thenucleation process is terminated. Whether or not a specified amount ofnuclei have been generated is determined by the amount of metal saltsadded to the nucleation aqueous solution.

The amount of nuclei generated in the nucleation process is notparticularly limited, however, in order to obtain a composite hydroxidehaving good particle size distribution, the amount is preferably 1% to2%, and more preferably 1.5% or less than the overall amount, or inother words the amount of metal salts supplied for obtaining thecomposite hydroxide.

When obtaining a nickel composite hydroxide having dense structure, inthe nucleation process, the crystallization reaction is performed in anon-oxidizing atmosphere in which the oxygen concentration is 1 volume %or less, and the agitation speed inside the reaction tank is properlyadjusted so that the agitation power requirement per unit volume ofreaction solution is in the range 0.5 kW/m³ to 4 kW/m³. In this way,when oxidation during nucleation is suppressed and agitation is properlyadjusted, the nuclei clump together and the particle size becomes large,so it is possible to generate relatively dense large nuclei.

On the other hand, when obtaining a nickel composite hydroxide havingdouble structure, in the nucleation process the crystallization reactionis performed in an oxidizing atmosphere in which the oxygenconcentration exceeds 1 volume %, and the agitation speed inside thereaction tank is properly adjusted so that the agitation powerrequirement per unit volume of reaction solution is in the range 0.5kW/m³ to 4 kW/m³. In this way, by performing nucleation in an oxidizingatmosphere and properly adjusting the agitation, minute primaryparticles clump together to form nuclei.

(Particle Growth Process)

After the nucleation process, the pH value of the nucleation solution isadjusted at a standard solution temperature of 25° C. to be 10.5 to12.0, and preferably 11.0 to 12.0, which is a pH value that is lowerthan the pH value during the nucleation process, and an aqueous solutionfor particle growth, which is the reaction aqueous solution in theparticle growth process is obtained. More specifically, control of thepH during this adjustment is performed by adjusting the amount of alkaliaqueous solution that is supplied.

By adjusting the pH value of the aqueous solution for particle growth soas to be within the range above, the nuclei grow reaction preferentiallyoccurs over the nucleation reaction, and during the particle growthprocess hardly any new nuclei are generated in the aqueous solution forparticle growth, so nuclei growth (particle growth) occurs, and acomposite hydroxide having a specified particle size is formed.

Similarly, as particle growth occurs by supplying mixed aqueoussolution, the pH value and ammonium ion density of the aqueous solutionfor particle growth change, so control is performed by supplying mixedaqueous solution, alkali aqueous solution and ammonia aqueous solutionto the aqueous solution for particle growth in order to keep the pHvalue of the aqueous solution for particle growth in a range of 10.5 to12.0 and the ammonium ion density in a range of 3 g/L to 25 g/L at astandard solution temperature of 25° C.

Then, at the instant when the particles of the composite hydroxide havegrown to a specified particle size, the particle growth process isterminated. The particle size of the composite hydroxide can be easilydetermined from the amount of metal salts added in each process, byfinding the relationship in preliminary testing between the amount ofmetal salts added to each reaction solution in both the nucleationprocess and particle growth process and the particles obtained.

In this way, in the case of the method for manufacturing compositehydroxide as described above, the nuclei are preferentially generated inthe nucleation process, and hardly any nuclei growth occurs, andconversely, in the particle growth process, only nuclei growth occurs,and hardly any new nuclei are generated. Therefore, in the nucleationprocess, it is possible to form homogeneous nuclei having a narrowparticle size distribution range, and in the particle growth process, itis possible to grow the nuclei homogeneously. Therefore, in the methoddescribed above for manufacturing composite hydroxide, it is possible toobtain homogeneous nickel composite hydroxide having a narrow particlesize distribution range.

In the case of the manufacturing method described above, in bothprocesses, the metal ions become a composite hydroxide and arecrystallized, so the ratio of the liquid component with respect to themetal component in both reaction aqueous solutions increases. In thatcase, it is apparent that the density of the mixed aqueous solution thatis supplied is decreased, and particularly in the particle growthprocess, there is a possibility that composite hydroxide will not besufficiently grown.

Therefore, in order to suppress an increase in the liquid componentdescribed above, preferably part of the liquid component in the aqueoussolution for particle growth is discharged to outside of the reactiontank during the particle growth process after the nucleation processends. More specifically, the supply of mixed aqueous solution, alkaliaqueous solution and ammonia aqueous solution to the aqueous solutionfor particle growth and the agitation thereof is stopped, the nuclei andcomposite hydroxide are precipitated out, and the supernatant liquid ofthe aqueous solution for particle growth is discharged. As a result, itis possible to increase the relative density of the mixed aqueoussolution in the aqueous solution for particle growth. In a state of highrelative density of mixed aqueous solution, it is possible to grow thecomposite hydroxide, and thus it is possible to make the particle sizedistribution of the composite hydroxide narrower, and increase theoverall density of secondary particles of composite hydroxide.

Moreover, in the embodiment illustrated in FIG. 1, the pH of thenucleation aqueous solution when the nucleation process has ended isadjusted and an aqueous solution for particle growth is formed so thatthe particle growth process can be performed following the nucleationprocess, so there is an advantage in that transition to the particlegrowth process can be performed quickly. Furthermore, there is anadvantage in that transition from the nucleation process to the particlegrowth process can be easily performed by only adjusting the pH, andadjustment of the pH can also be performed easily by temporarilystopping supply of the alkali aqueous solution. The pH of the reactionaqueous solution can be adjusted by adding the same kind of inorganicacid as the acid of the metal compound, for example, in the case of asulfate, by adding sulfuric acid to the reaction aqueous solution.

However, as in another embodiment illustrated in FIG. 2, it is alsopossible to form a component adjusted aqueous solution separate from thenucleation aqueous solution in which the pH and ammonium ion densityhave been adjusted to be suitable for the particle growth process, andto form a reaction aqueous solution by adding an aqueous solutioncontaining nuclei that were generated by performing nucleation in aseparate reaction tank (nucleation aqueous solution, or preferably anaqueous solution obtained by removing part of the liquid component fromthe nucleation aqueous solution) to this component adjusted aqueoussolution, and then perform the particle growth process by using thisreaction aqueous solution as the aqueous solution for particle growth.

In this case, separation of the nucleation process and the particlegrowth process can be more definitely performed, so the state of thereaction aqueous solutions during each process can be set to the optimumconditions for each process. Particularly, from the starting point ofthe particle growth process, it is possible to set the pH of the aqueoussolution for particle growth to the optimum conditions, so the nickelcomposite hydroxide that is formed in the particle growth process ismore homogeneous and has a narrower particle size distribution.

When obtaining a nickel composite hydroxide having dense structure, inthe particle growth process, the crystallization reaction is performedwhile maintaining a non-oxidizing atmosphere, and by properly adjustingthe agitation speed in the reaction tank so that the agitation powerrequirement per unit volume of the reaction aqueous solution is within arange 0.5 kW/m³ to 4 kW/m³. In this way, when oxidation during particlegrowth is suppressed and the agitation is properly adjusted, growth ofprimary particles is promoted, and therefore the moderately largesecondary particles with the large and dense primary particles areformed.

On the other hand, when obtaining a nickel composite hydroxide havingdouble structure, at the start of the particle growth process (range of0% to 40% with respect to the overall time of the particle growthprocess), the crystallization reaction is performed while maintaining anoxidizing atmosphere and by properly adjusting the agitation speed inthe reaction tank so that the agitation power requirement per unitvolume of the reaction aqueous solution is within a range 0.5 kW/m³ to 4kW/m³, after which the atmosphere is changed from an oxidizingatmosphere to a non-oxidizing atmosphere, and the crystallizationreaction is continued. By using an oxidizing atmosphere at the start ofthe particle growth process in this way, clumping together of the minuteprimary particles is promoted more than growth of the primary particles,and a center section having low density of minute primary particles withmany gaps is formed; then after that, by changing to a non-oxidizingatmosphere, growth of primary particles which are crystallized on theoutside of that center section is promoted, forming a highly denseouter-shell section having large primary particles.

Next, the agitation power requirement, control of the pH, and control ofthe reaction atmosphere in each process, materials and solutions used ineach process, and reaction conditions will be explained in detail.

(Agitation Power Requirement)

In the present invention, the particle size of the nickel compositehydroxide is adjusted, as well as by controlling the pH value in thenucleation process, the amount of raw materials added for nucleation andthe time of the particle growth process, by controlling at least theagitation of the reaction aqueous solution during the nucleationprocess.

In the present invention, the reaction aqueous solution is controlled bycontrolling the agitation power requirement per unit volume of reactionaqueous solution during the nucleation process and particle growthprocess described above. More specifically, in order to perform controlso that the average particle size of the nickel composite hydroxide isgreater than 7 μm and equal to or less than 15 μm, it is necessary tocontrol at least the agitation power requirement per unit volume of thereaction aqueous solution in the nucleation process so as to be 0.5kW/m³ to 4.0 kW/m³, and preferably 0.6 kW/m³ to 3.5 kW/m³, and even morepreferably 0.8 kW/m³ to 3.0 kW/m³.

Conventionally, in the crystallization reaction, the particle size ofthe nickel composite hydroxide was mainly controlled by controlling thepH value in the nucleation process, the amount of raw material added fornucleation, and the time of the particle growth process, and in regardsto the agitation of the reaction aqueous solution, the agitation powerrequirement was set to nearly 4.5 kW/m³ to 7.0 kW/m³ from only theaspect of uniformly dispersing the components in the reaction tank andthe aspect of uniformly dispersing the raw material that is supplied.Therefore, the particle size of the nickel composite hydroxide that isobtained remains at around 7 μm.

During both nucleation and particle growth, it is important to have thesecondary particles formed by aggregated primary particles further clumptogether with each other in order to cause the secondary particles togrow to a specified particle size. However, when agitation of thereaction aqueous solution is excessive, aggregation of secondaryparticles that is necessary for growth of the secondary particlesseparates, so it seems that it will be difficult for the secondaryparticles to grow to exceed 7 μm. Therefore, in the present invention,agitation is regulated to the extent that the components in the reactiontank are uniform, and so that growth of the secondary particles to aspecified particle size is not inhibited, or in other words so thataggregation of particles formed by aggregated primary particles are notinhibited, so the agitation power requirement is controlled within therange described above, and the average particle size of the secondaryparticles of the nickel composite hydroxide that is obtained is kept ina range greater than 7 μm.

When the agitation power requirement is less than 0.5 kW/m³, agitationis insufficient, so the components in the reaction tank becomenon-uniform, the particle size distribution becomes large, thecomposition becomes unstable, as well as coarse particles are generated,and the average particle size of the composite hydroxide that isobtained may exceed 15 μm. On the other hand, when the agitation powerrequirement is greater than 4 kW/m³, the secondary particles that wereonce clumped together become separated as described above, and itbecomes impossible to sufficiently grow the secondary particles.

However, as long as the secondary particles have been sufficientlygrown, the secondary particles will not separate even when the agitationpower requirement is greater than 4 kW/m³, and the supplied raw fluidsare uniformly dispersed, so when the average particle size is greaterthan 7 μm and equal to or less than 15 μm, it is possible to obtaincomposite hydroxide having a sharp particle size distribution.

Such agitation power requirement can be the same in both the nucleationprocess and the particle growth process, however, when obtaining nickelhydroxide having a dense structure, control can be performed so that theagitation power requirement in a non-oxidizing atmosphere in thenucleation process is 0.5 kW/m³ to 4.0 kW/m³, and in the particle growthprocess is 4.0 kW/m³ to 10 kW/m³. By performing this kind of control, inthe nucleation process, nuclei do not grow, however, the primaryparticles are large, and the particle size of the nuclei themselvesbecomes large, so it is possible to generate relatively dense and largenuclei. Moreover, in the particle growth process, by secondary particlesclumping together while dense primary particles are generated on thesurface of the nuclei that were obtained in the nucleation process, itbecomes possible to make the particle size of the secondary particleslarge. Furthermore, in the latter half of the particle growth process,primary particles are grown so as to fill gaps in the grape-like tuftshaped particles formed by the aggregated secondary particles; andfinally, it is possible to obtain relatively dense secondary particleshaving a large particle size and nearly spherical shape. Also, in thehigh-density area where aggregation is insufficient due to the increasein particle density, it is possible to suppress the particle sizedistribution from becoming bad due to new nucleation.

On the other hand, in the case of obtaining nickel hydroxide havingdouble structure, under the oxidizing atmosphere in the nucleationprocess and in the primary stage of the particle growth process, it ispossible for the agitation power requirement to be controlled so as tobe 0.5 kW/m³ to 4.0 kW/m³, and during the crystallization reaction underthe non-oxidizing atmosphere of the particle growth process, theagitation power requirement can be controlled so as to be 4.0 kW/m³ to10 kW/m³. By performing this kind of control, the size and number ofnuclei are adequately controlled in the nucleation process. Moreover, inthe initial stage of the particle growth process, minute primaryparticles clump together, but low-density secondary particles havingmany gaps are formed. After that, by changing the reaction atmosphereand agitation power requirement, large primary particles clump aroundthe low density secondary particles, and an outer-shell section isformed by the high density aggregated particles; then in the latter halfof the particle growth process, primary particles are grown so as tofill gaps in the grape-like tuft shaped particles formed by theaggregated particles of the outer-shell section; and finally, it ispossible to obtain secondary particles having a large particle size andnearly spherical shape, and having a double structure in which thecenter section has a low density composed of minute primary particles,and the outer-shell section has a high density composed of large primaryparticles.

(pH Control)

In the nucleation process, it is necessary to control the pH value ofthe reaction aqueous solution so that at a standard solution temperatureof 25° C. the pH value is in the range 12.0 to 14.0, and preferably 12.3to 13.5. When the pH value is greater than 14.0, the nuclei that aregenerated are too small, so there is a problem in that the reactionaqueous solution becomes a gel. Moreover, when the pH value is less then12.0, a nuclei growth reaction occurs at the same time that nuclei areformed, so the range of the particle size distribution of the nucleiformed becomes large and non-homogenous. In other words, in thenucleation process, by controlling the pH value of the reaction aqueoussolution so as to be in the range above, it is possible to suppressnuclei growth, so that only nuclei are generated, and thus it ispossible to keep the nuclei that are formed homogeneous and the range ofthe particle size distribution narrow.

On the other hand, in the particle growth process, it is necessary tocontrol the pH value of the reaction aqueous solution so that at astandard solution temperature of 25° C. the pH value is in the range10.5 to 12.0, and preferably 11.0 to 12.0. When the pH value is greaterthan 12.0, there is a large amount of newly generated nuclei, and theminute secondary particles are generated, so it is not possible toobtain a hydroxide having a good particle size distribution. Moreover,when the pH value is less than 10.5, the solubility due to ammonium ionsbecomes high, and the amount of remaining metal ions in the solutionthat do no precipitate out increases, so productivity becomes bad. Inother words, in the particle growth process, by controlling the pH valueof the aqueous solution so as to be in the range described above, it ispossible to preferentially cause only the nuclei that were generated inthe nucleation process to grow, and to suppress the generation of newnuclei, and thus it is possible to obtain a nickel composite hydroxidethat is homogeneous and that has a narrow particle size distribution.

In both the nucleation process and the particle growth process, therange of fluctuation of the pH value is preferably the set value ±0.2 orless. When the range of fluctuation of the pH value is large, nucleationand particle growth do not become constant, so it may not be possible toobtain a nickel composite hydroxide having a narrow particle sizedistribution range.

A pH value of 12 is the boundary condition between nucleation andparticle growth, so depending on whether or not there are nuclei in thereaction aqueous solution, it is possible to designate the condition foreither the nucleation process or the particle growth process.

In other words, after the pH value in the nucleation process iscontrolled so as to be higher than 12 and a large amount of nuclei aregenerated, next, in the particle growth process, when the pH value is12, there is a large amount of nuclei in the reaction aqueous solution,so nuclei growth preferentially occurs, and hydroxide is obtained thathas a narrow particle size distribution and has a relatively largeparticle size.

On the other hand, in a state in which nuclei do not exist in thereaction aqueous solution, or in other words, when the pH value in thenucleation process is 12, there are no growing nuclei, so nucleationpreferentially occurs, and by making the pH value in the particle growthprocess less than 12, the generated nuclei grow and a good hydroxide canbe obtained.

In either case, the pH value in the particle growth process should becontrolled so as to be lower than the pH value in the nucleationprocess, and in order for there to be a clear division betweennucleation and particle growth, preferably the pH value in the particlegrowth process is less than the pH value in the nucleation process by avalue of 0.5 or more, and more preferably less by a value of 1.0 ormore.

(Reaction Atmosphere)

The particle size and particle structure of the nickel compositehydroxide of the present invention are also controlled by the reactionatmosphere in the nucleation process and particle growth process.

When the atmosphere inside the reaction tank during both processesdescribed above is controlled so as to be a non-oxidizing atmosphere,growth of the primary particles that form the nickel composite hydroxideis promoted, and secondary particles are formed having primary particlesthat are large and dense, with the particle size being moderately large.Particularly, in both processes, by making the non-oxidizing atmospheresuch that the oxygen concentration is 1 volume % or less, and preferably0.5 volume % or less, and even more preferably 0.3 volume % or less,nuclei having relatively large primary particles can be generated in thenucleation process, and it is possible for nuclei to clump together toform relatively dense and large nuclei, so such a state is preferred.

Moreover, in the particle process as well, large primary particles aregenerated around the nuclei that were generated in the nucleationprocess, and together with the particles growing, particle growth ispromoted by the clumping together of growing particles, and thus it ispossible to obtain dense and moderately large secondary particles.

As methods for maintaining the space inside the reaction tank at such anatmosphere, there is a method of letting an inert gas such as nitrogenflow into the space inside the reaction tank, and further causingbubbling of the inert gas in the reaction solution.

On the other hand, when trying to obtain a cathode active materialhaving hollow structure, by performing control so that the reactionatmosphere during the nucleation process and in the initial stage of theparticle growth process is an oxidizing atmosphere, the center sectionof minute particles described above will be low density, and after that,by performing control so that the reaction atmosphere falls in a rangefrom a weak oxidizing atmosphere to a non-oxidizing atmosphere, it ispossible to form a high-density outer-shell section having large anddense primary particles. More specifically, in part of the oxidizingatmosphere during the nucleation process and in the initial stage of theparticle growth process, the oxygen concentration of the space insidethe reaction tank is 1 volume % or greater, or preferably 2 volume % orgreater, and even more preferably 10 volume % or greater. Particularly,an air atmosphere (oxygen concentration: 21 volume %) that is easilycontrolled is preferred. By making the atmosphere such that the oxygenconcentration is 1 volume % or greater, it is possible to generateminute particles having an average particle size of 0.01 μm to 0.3 μm.However, when the oxygen concentration is 1 volume % or less, theaverage particle size of the primary particles in the center section maybecome greater than 0.3 μm. The upper limit for the oxygen concentrationis not particularly limited, however, when the oxygen concentrationexceeds 30 volume %, the average particle size of the primary particlesabove may become less than 0.01 μm, and is not desirable.

On the other hand, the non-oxidizing atmosphere after changing is suchthat the oxygen concentration of the space inside the reaction tank is 1volume % or less, and preferably is 0.5 volume % or less, and even morepreferably is 0.2 volume % or less. This kind of atmosphere iscontrolled by mixing inert gas with the oxygen. By causing particles togrow by making the oxygen concentration of the space inside the reactiontank 1 volume % or less, it is possible to suppress unnecessaryoxidation of the particles, as well as it is possible to promote growthof primary particles that will be larger than those of the centersection and that will have a uniform particle size, and as a result, itis possible to obtain secondary particles having a highly denseouter-shell section.

The timing for changing the atmosphere in the particle growth processabove is determined considering the size of the center section of thenickel composite hydroxide so that the adequate hollow sections can beobtained that is large enough that minute particles are generated andthus the cycle characteristics thereof do not become bad. For example,of the overall time of the particle growth process, the change ispreferably performed at a time within a range from 0% to 40%, morepreferably performed within the range from 0% to 30%, and even morepreferably within a range from 0% to 25% from the start of the particlegrowth process. When the change is performed at a time that exceeds 40%of the overall time of the particle growth process, the center sectionthat is formed will be large, and the thickness of the outer-shellsection with respect to the particle size of the secondary particleswill become too thin. On the other hand, in the case that the change isperformed before the start of the particle growth process, or in otherwords, during the nucleation process, the center section will be toosmall, or secondary particles having the structure described above willnot be formed.

When maintaining the reaction atmosphere as a non-oxidizing atmosphere,or when changing the atmosphere from an oxidizing atmosphere to anon-oxidizing atmosphere, normally the primary particles have a plateshape and/or needle shape in the crystallization reaction for which theatmosphere is controlled as described above. However, the primaryparticles of the nickel composite hydroxide described above, dependingon the composition thereof, may rectangular, elliptical, rhombohedronand the like.

In the following, conditions such as the metal compound, the ammoniaconcentration in the reaction aqueous solution, the reaction temperatureand the like will be explained, however, the difference in the reactionaqueous solutions of the nucleation process and the particle growthprocess is only the range in which the pH of the reaction aqueoussolution is controlled, and the conditions such as the metal compound,the ammonia concentration in the reaction aqueous solution, the reactiontemperature and the like are essentially the same in both processes.

(Metal Compounds)

As the metal compounds, compounds that include the objective metal areused. Preferably the compounds that are used are compounds that arewater-soluble, and could be for example, a nitrate, a sulfate, ahydrochloride and the like. For example, preferably nickel sulfate,manganese sulfate, and cobalt sulfate are used.

(Additional Elements)

For the additional elements (one or more kinds of elements selected fromamong Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W), preferably water-solublecompounds are used, for example, titanium sulfate, ammoniumperoxotitanic acid, potassium titanium oxalate, vanadium sulfate,ammonium vanadate, chromium sulfate, potassium chromate, zirconiumsulfate, zirconium nitrate, niobium oxalate, ammonium molybdate, sodiumtungstate, ammonium tungstate and the like can be used.

When uniformly dispersing the additional elements into the compositehydroxide, an aqueous solution in which salts that include the one ormore additional elements are dissolved is added to the mixed aqueoussolution in the nucleation process and the particle growth process, oran aqueous solution, in which salt that includes the one or moreadditional elements is dissolved, and the mixed aqueous solution aresimultaneously supplied into the crystallization tank, which makes itpossible to precipitate out the uniformly dispersed additional elementsinto the composite hydroxide.

Moreover, when coating the surface of the composite hydroxide with theadditional elements, it is possible to uniformly coat the surface withthe additional elements, for example, by making a slurry of thecomposite hydroxide using an aqueous solution that includes theadditional elements, and then while controlling the pH value to aspecified value, adding an aqueous solution that includes the one ormore kinds of additional elements to deposit the additional elementsonto the surface of the composite hydroxide by a crystallizationreaction. In this case, instead of an aqueous solution that includes theadditional elements, it is possible to use an alkoxide solution of theadditional elements. Furthermore, it is also possible to coat thesurface of the composite hydroxide with additional elements by applyingan aqueous solution or slurry that includes the additional elements andthen drying. Moreover, it is possible to coat the surface of thecomposite hydroxide by a method such as spray drying a slurry in whichsalts that include the composite hydroxide and one or more kinds ofadditional elements are suspended, or by mixing salts that include thecomposite hydroxide and one or more kinds of additional elements by asolid phase method.

When coating the surface with additional elements, by reducing theatomic ratio of additional element ions that exist in the mixed aqueoussolution by just the amount of coating, it is possible to match thatatomic ratio with the atomic ratio of metal ions of composite hydroxideto be obtained. Moreover, the process of coating the surface ofparticles with additional elements can be performed on the particlesafter heat treatment of the composite hydroxide.

(Concentration of Mixed Aqueous Solution)

The concentration of the mixed aqueous solution, for the total metalcompound, is preferably 1 mol/L to 2.6 mol/L, and more preferably 1.5mol/L to 2.4 mol/L, and even more preferably 1.8 mol/L to 2.2 mol/L.When the concentration of mixed aqueous solution is less than 1/mol/L,the amount of crystallization per reaction tank is reduced, so there isa decrease in productivity, and thus is not desirable. On the otherhand, when the concentration of mixed aqueous solution is greater than2.6 mol/L, the solution freezes at −5° C. or less and there is a dangerof the pipes in the equipment becoming clogged, so it is necessary tomaintain the heat in the pipes or heat the pipes, which costs.

Moreover, the metal compound does not absolutely need to be supplied tothe reaction tank as a mixed aqueous solution, for example, when metalcompounds, in which the compounds are generated when a reaction occurswhen mixed, are used, the metal compound aqueous solutions can beseparately adjusted so that the concentration of the total metalcompound aqueous solution is within the range described above, and themetal compound aqueous solutions can be simultaneously supplied to thereaction tank at a specified ratios as individual metal compound aqueoussolutions.

Furthermore, the amount that mixed aqueous solution or individual metalcompound aqueous solutions are supplied to the reaction tank ispreferably such that the concentration of crystallized material at theinstant when the crystallization reaction ends is roughly 30 g/L to 200g/L, and preferably 80 g/L to 150 g/L. This is because when theconcentration of crystallized material is less than 30 g/L, theaggregation of primary particles is insufficient, and when theconcentration exceeds 200 g/L, dispersion in the reaction tank of themixed aqueous solution that is added is not sufficient, and deviationoccurs in the particle growth.

(Complexing Agent)

In the method for manufacturing the composite hydroxide above,preferably a non-reducible complexing agent is used. When a complexingagent that has reducibility is used, the solubility of manganese in thereaction aqueous solution becomes too large, and a nickel compositehydroxide having high tap density cannot be obtained. The non-reduciblecomplexing agent that is used is not particularly limited, and can beany agent as long as the agent can bond in aqueous solution with nickelions, cobalt ions and manganese ions to form complexes. For example, theagent could be an ammonium ion donor, ethylenediamine tetraacetic acid,nitrito triacetic acid, uracil diacetic acid, or glycine.

The ammonium ion donor is not particularly limited, however, forexample, it is possible to use ammonia, ammonium sulfate, ammoniumchloride, ammonium carbonate, ammonium fluoride and the like.

(Ammonia Concentration)

The ammonia concentration in the reaction aqueous solution is maintainedat a constant value preferably within the range 3 g/L to 25 g/L, andmore preferably 5 g/L to 20 g/L and even more preferably 5 g/L to 15g/L.

Ammonia becomes ammonium ions and functions as a complexing agent, sowhen the ammonia concentration is less than 3 g/L, it is not possible tokeep the solubility of metal ions constant, plate shaped primaryparticles of hydroxide having a uniform shape and particle size are notformed, and it becomes easy for gel shaped nuclei to be generated, so itbecomes easy for the particle size distribution to spread.

On the other hand, when the ammonia concentration is greater than 25g/L, the solubility of metal ions becomes large, and the formedhydroxide is dense, so the cathode active material for anonaqueous-electrolyte secondary battery may also have a dense structurewith a small particle size and low specific surface area. Moreover, whenthe solubility of metal ions becomes too large, the amount of metal ionsremaining in the reaction aqueous solution increases, and changes in thecomposition occur.

When the ammonia concentration fluctuates, the solubility of the metalions fluctuates, and a uniform hydroxide cannot be formed, so preferablythe ammonia concentration is maintained at a constant value. Forexample, preferably the ammonia concentration is maintained at a desiredconcentration with the width between the upper limit and the lower limitbeing 5 g/L.

(Reaction Solution Temperature)

Inside the reaction tank, the temperature of the reaction solution ispreferably set to 20° C. to 60° C., and more preferably to 35° C. to 60°C. When the temperature of the reaction solution is less than 20° C.,the solubility of metal ions is low, so nuclei are easily generated andcontrol becomes difficult. However, when the temperature is greater than60° C., the volatilization of ammonia is promoted, so in order tomaintain a specified ammonia concentration, a large amount of ammoniumion donor must be added, and thus the cost increases.

(Alkali Aqueous Solution)

The alkali aqueous solution that adjusts the pH of the reaction aqueoussolution is not particularly limited, and, for example, it is possibleto use an alkali metal hydroxide aqueous solution such as sodiumhydroxide, potassium hydroxide and the like. In the case of using analkali metal hydroxide, the alkali metal hydroxide can be directlysupplied into the reaction aqueous solution, however, due to the ease ofcontrolling the pH of the reaction aqueous solution in the reactiontank, preferably the alkali metal hydroxide is added to the reactionaqueous solution inside the reaction tank as an aqueous solution.

The method for adding the alkali aqueous solution to the reaction tankis not particularly limited, however, should be added while sufficientlystirring the reaction aqueous solution and using a pump that is capableof flow control, such as a metering pump, so that the pH value of thereaction aqueous solution is maintained within a specified range.

(Manufacturing Equipment)

In the manufacturing method for the composite hydroxide of the presentinvention, an apparatus that does not collect the product until thereaction is complete is used. For example, the apparatus include anormally used batch reaction tank in which a mixer has been installed.By using this apparatus, there is no problem of the growing productbeing collected at the same time as the overflow as in the case of acontinuous crystallizer that collects the product by a typical overflow,so it is possible to obtain particles that have a uniform particle sizeand a narrow particle size distribution.

Moreover, it is necessary to control the reaction atmosphere, so anapparatus that is capable of controlling the atmosphere, such as adirect vent type of apparatus is used. By using this kind of apparatus,it is possible to obtain composite hydroxide having the structuredescribed above, as well as it is possible to nearly uniformly proceedwith the nucleation reaction and particle growth reaction, so it ispossible to obtain particles having an excellent particle sizedistribution, or in other words, particles having a narrow particle sizedistribution.

2.1. Cathode Active Material for a Nonaqueous-Electrolyte SecondaryBattery

(Composition)

The cathode active material of the present invention is a lithium nickelcomposite oxide, and the composition thereof is adjusted so as to beexpressed by the following general expression.Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂  General Expression:

(−0.05≤u≤0.50, x+y+z+t=1, 0.3≤x, 0≤y≤0.55, 0≤z≤0.4, 0≤t≤0.1, and M isone or more kind of additional element that is selected from among Al,Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W)

Particularly, when the cathode active material has a hollow structure,the composition is adjusted so as to be expressed by the followinggeneral expression, or in other words, preferably the amount of nickelcontained is reduced, and the amount of manganese contained isincreased.Li_(1+u)Ni_(x)Mn_(y)Co_(z)M_(t)O₂  General Expression:

(−0.05≤u≤0.50, x+y+z+t=1, 0.3≤x, 0.1≤y≤0.55, 0≤z≤0.4, 0≤t≤0.1, and M isone or more kind of additional element that is selected from among Al,Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W)

In the cathode active material of the present invention, the value “u”indicates the excessive amount of lithium and is within the range −0.05to 0.5. When the excessive amount of lithium “u” is less than −0.05, thereaction resistances of the cathode in the nonaqueous-electrolytesecondary battery that uses the obtained cathode active material becomeslarge, so the output of the battery becomes low. On the other hand, whenthe excessive amount of lithium “u” is greater than 0.50, the initialdischarge capacity when the cathode active material above is used in thecathode of a battery decreases, and the reaction resistance of thecathode increases.

In order to further reduce the reaction resistance, the excessive amountof lithium “u” is preferably 0 or greater, more preferably 0 or greaterand 0.35 or less, and even more preferably 0 or greater and 0.20 orless. From the aspect of increasing capacity, when the value “x” thatindicates the nickel content is 0.7 or less and the value “y” is 0.1 orgreater in the general expression above, the excessive amount of lithium“u” is preferably 0.10 or greater.

The value “y” that indicates the manganese content is 0 or greater and0.55 or less, however, in order for the cathode active material of thepresent invention to have a hollow structure, the value “y” is 0.1 orgreater and 0.55 or less. When the value “y” is within such a range, thenickel composite hydroxide, which is a precursor, has a structure havinga center section that is composed of minute primary particles, and anouter-shell section that is composed of primary particles on the outsideof the center section that are larger than the minute primary particles.When the manganese content “y” is greater than 0.55, there is a problemin that the capacity of a battery that uses the cathode active materialdecreases.

Moreover, as expressed by the general expression above, more preferablythe cathode active material of the present invention is adjusted so thatthe lithium nickel composite oxide includes additional elements. Byincluding the additional elements above, it is possible to improve thedurability and the output characteristics of a battery that uses thismaterial as cathode active material.

Particularly, by uniformly distributing the additional elements on thesurface of or inside the particles, it is possible to obtain the effectabove for all particles, and thus it is possible to obtain the effectabove by adding a small amount, as well as suppress a decrease incapacity.

Furthermore, in order to obtain the effect by adding even a smalleramount, preferably the concentration of additional elements on thesurface of the particles is greater than on the inside of the particles.

When the atomic ratio “t” of the additional elements M with respect toall atoms is greater than 0.1, the metal elements that contribute to theRedox reaction decrease, so the battery capacity decreased, which is notdesirable. Therefore, the atomic ratio “t” of the additional elements Mis adjusted so as to be within the range above.

(Average Particle Size)

The cathode active material of the present invention is such that theaverage particle size is greater than 8 μm and equal to or less than 16μm, and preferably greater than 8 μm and equal to or less than 12 μm.When the average particle size is equal to or less than 8 μm, the tapdensity decreases, the packing density of particles with forming acathode decreases and the battery capacity per volume of the cathodedecreases. On the other hand, when the average particle size is greaterthan 16 μm, the specific surface area of the cathode active materialdecreases, and due to a decrease in the boundary surface with theelectrolyte of the battery, the resistance of the cathode increases, andthe output characteristics of the battery decrease.

Therefore, by adjusting the cathode active material of the presentinvention to within the range above, it is possible to increase thebattery capacity per volume in a battery that uses the cathode activematerial in the cathode, as well as it is possible to obtain excellentbattery characteristics such as good safety and high output.

(Particle Size Distribution)

The cathode active material of the present invention is made ofsecondary particles of a lithium nickel composite oxide having extremelyhigh homogeneity in which the index [(d90−d10)/Average particle size]that indicates the expanse of the particle size distribution is 0.60 orless, and preferably 0.55 or less. When the particle size distributioncovers a large range, many minute particles that have a very smallparticle size with respect to the average particle size, and many coarseparticles that have a very large particle size with respect to theaverage particle size exist in the cathode active material. When acathode is formed using a cathode active material in which there aremany minute particles, there is a possibility that local reactions ofthe minute particles will occur and generate heat, and thus togetherwith a decrease in safety, the minute particles selectively deteriorate,causing the cycle characteristics to become bad. On the other hand, whena cathode is formed using a cathode active material in which there aremany coarse particles, there is not sufficient reaction area between theelectrolyte and the cathode active material, and thus the battery outputdecreases due to an increase in reaction resistance.

Therefore, by making the index [(d90−d10)/Average particle size] of theparticle size distribution of the cathode active material to be 0.60 orless, it is possible to reduce the ratio of minute particles and coarseparticles, and a battery in which this cathode active material is usedfor the cathode has excellent safety, good cycle characteristics andgood battery output. The average particle size, d90 and d10 are the sameas used in the composite hydroxide, and measurement can also beperformed in the same way.

As in the case of the composite hydroxide, which was a precursor, it isconfirmed that classifying the cathode active material into a widenormal distribution, and obtaining a cathode active material having anarrow particle distribution is difficult.

(Tap Density)

For the cathode active material above, the tap density, which is anindex of the packing density when tapping is performed, is preferably1.8 g/cm³ or greater, and more preferably 2.0 g/cm³ or greater.

In consumer products or in electric automobiles, increasing the batterycapacity in order to increase the usable time of a battery or thetravelable distance is an important problem, and there is a need to notonly increase the capacity of the active material itself, but also topack a larger amount of active material as electrodes. On the otherhand, the thickness of the electrodes of a secondary battery, due to theproblem of packing for the overall battery, or due to the problem ofelectron conductivity, is only tens of microns. Particularly, when thetap density is less than 1.8 g/cm³, the amount of active material thatcan be put inside the limited volume of the electrodes decreases, so itis not possible to make the capacity of the overall secondary batteryhigh.

The upper limit of the tap density is not particularly limited, however,the upper limit under normal manufacturing conditions is about 3.0g/cm³.

(Specific Surface Area)

When the cathode active material above has dense solid structure, thespecific surface area is preferably 1.5 m²/g or less, and morepreferably 1.2 m²/g or less. When the specific surface area is greaterthan 1.5 m²/g, the average particle size becomes too small, and it isnot possible to obtain particles having a tap density of 1.8 g/cm³. Thelower limit of the specific surface area is not particularly limited,however, is preferably 0.2 m²/g or greater, and more preferably 0.5 m²/gor greater. When the specific surface area becomes less than 0.2 m²/g,it is possible that when the cathode active material of the presentinvention is used in a nonaqueous-electrolyte secondary battery, thecontact with the electrolyte material will decrease, and thus there willbe a decrease in battery capacity.

On the other hand, in the case of hollow structure, the specific surfacearea is preferably 0.8 m²/g to 2.0 m²/g. In the case of this kind ofhollow structure and the same average particle size, it is possible toincrease the specific surface area over that of the solid structure.When the specific surface area is greater than 2.0 m²/g, the averageparticle size becomes too small, and the amount of active material thatcan be packed inside a battery having limited capacity decreases, so thecapacity per volume of the battery decreases. The lower limit of thespecific surface area is not particularly limited, however, incomparison with the solid structure, is preferably 0.8 m²/g or greater.

(Characteristics)

When the cathode active material above is used, for example, in thecathode of a 2032 type coin battery, a high initial discharge capacityof 150 mAh/g or greater, low cathode resistance, and a high cyclecapacity maintenance rate are obtained, indicating excellentcharacteristics as a cathode active material for anonaqueous-electrolyte secondary battery.

2.2. Manufacturing Method of a Cathode Active Material for aNonaqueous-Electrolyte Secondary Battery

The manufacturing method of a cathode active material of the presentinvention is not particularly limited as long as the method is able tomanufacture a cathode active material having the average particle size,the particle size distribution, particle structure and compositiondescribed above, however, by employing the method below, it is possibleto more surely manufacture such a cathode active material, so ispreferred.

The manufacturing method of the cathode active material of the presentinvention includes a mixing process of mixing as raw materials nickelcomposite hydroxide and a lithium compound, to form a lithium mixture,and a calcination process of calcining the mixture that was formed inthe mixing process, however, before the mixing process, it is possibleto have a heat treatment process of heat treating the nickel compositehydroxide. In other words, as illustrated in FIG. 3, the manufacturingmethod can include: a) a heat treatment process of heat treating thenickel composite hydroxide that is a raw material of the cathode activematerial of this invention, b) a mixing process of mixing a lithiumcompound with the particles after heat treatment to form a lithiummixture, and c) a calcination process of calcining the mixture that wasformed in the mixing process. Each of the processes will be explainedbelow.

a) Heat Treatment Process

The heat treatment process is a process of performing heat treatment byheating the nickel composite hydroxide that was obtained by themanufacturing method of nickel composite hydroxide described above to atemperature of 105° C. to 750° C., and preferably 105° C. to 400° C. Byperforming this heat treatment process, moisture that is contained inthe composite hydroxide is removed. By performing this heat treatmentprocess, it is possible to reduce the moisture content that remains inthe particles up to the calcination process to a fixed amount.Therefore, it is possible to prevent fluctuation in the ratio of thenumber of atoms of metal and the number of atoms of lithium in thecathode active material that is manufactured and obtained.

The moisture content only needs to be removed to an amount so that thereis no fluctuation in the ratio of the number of atoms of metal and thenumber of atoms of lithium in the cathode active material, so it is notabsolutely necessary to convert all of the composite hydroxide to nickelcomposite oxide, and performing heat treatment at a temperature of 400°C. or less is sufficient, however, in order to further reducefluctuation, the heating temperature can be 400° C. or greater, so thatall of the composite hydroxide is converted to a composite oxide. In thecalcination process, which is a later process, conversion to a compositeoxide also occurs during heating, however, fluctuation is suppressed toa lesser extent than by this heat treatment.

In the heat treatment process, when the heating temperature is less than105° C., surplus moisture content in the composite hydroxide cannot beremoved, so it may not be possible to suppress the fluctuation above. Onthe other hand, when the heating temperature is greater than 750° C.,the particles are calcined by the heat treatment, and thus it is notpossible to obtain a composite oxide having a uniform particle size. Byfinding the metal component that is contained in the composite hydroxideaccording to heat treatment conditions in advance by analysis, andsetting the ratio with the lithium compound, it is possible to suppressthe fluctuation described above.

The atmosphere in which heat treatment is performed is not particularlylimited, and as long as the atmosphere is a non-reduced atmosphere, heattreatment is preferably performed in a current of air that can beperformed easily.

Moreover, the heat treatment time is not particularly limited, however,when the time is less than one hour, there is a possibility that removalof the surplus moisture in the composite hydroxide will not be performedsufficiently, so preferably the time is at least one hour or more, andpreferably 5 to 15 hours.

Moreover, the equipment used for heat treatment is not particularlylimited, and as long as the composite hydroxide can be heated in anon-reduced atmosphere, and preferably in an air current, an electricfurnace that does not generate gas can be suitably used.

b) Mixing Process

The mixing process is a process of mixing nickel composite hydroxide, ora composite hydroxide that was heat treated in the heat treatmentprocess described above (hereafter, may be referred to as “heat-treatedparticles”) with a material containing lithium, for example a lithiumcompound, to obtain a lithium mixture.

Here, not only a composite hydroxide from which residual moisturecontent was removed in the heat treatment process, but also compositeoxide that has been converted to an oxide in the heat treatment process,or mixtures of these particles are included in the heat-treatedparticles above.

Nickel composite hydroxide or heat-treated particles and lithiumcompound are mixed so that the ratio of the number of metal atoms otherthan lithium in the lithium mixture, or in other words, the total (Me)of the number of atoms of nickel, manganese, cobalt and additionalelements and the number of atoms of lithium (Li) (Li/Me) is 0.95 to 1.5,and preferably 1 to 1.35, and even more preferably 1 to 1.20. In otherwords, the ratio Li/Me does not normally change before or after thecalcination process, so the Li/Me ratio in this mixing process becomesthe Li/Me ratio of the cathode active material, so mixing is performedso that the Li/Me ratio in the lithium mixture becomes the same as theLi/Me ratio of the cathode active material to be obtained.

The lithium compound that is used for forming the lithium mixture is notparticularly limited, however, lithium hydroxide, lithium nitrate,lithium carbonate, or a mixture of these are easily obtained so arepreferred. Particularly, in consideration of the ease of handling andthe stability of quality, the use of lithium hydroxide or lithiumcarbonate or a mixture of these is even more preferred.

It is preferred that the lithium mixture be sufficiently mixed beforecalcination. In the case that the mixture is not sufficiently mixed,there is a possibility that a problem of fluctuation in the Li/Me ratiobetween individual particles will occur, and that sufficient batterycharacteristics will not be obtained.

Moreover, it is possible to use a typical mixer for mixing, for example,it is possible to use a shaker mixer, a lodige mixer, a julia mixer, a Vblender and the like, as long as the composite oxide or heat-treatedparticles and material containing lithium are sufficiently mixed to anextent that the structure of the nickel composite hydroxide is notdestroyed.

c) Calcination Process

The calcination process is a process of calcining the lithium mixturethat was obtained in the mixing process described above to form alithium nickel composite oxide. When the lithium mixture is calcined inthe calcination process, lithium that is in the material containinglithium is diffused into the nickel composite hydroxide or heat-treatedparticles, so a lithium nickel composite oxide is formed.

(Calcination Temperature)

Calcination of the lithium mixture is performed at 650° C. to 1000° C.When the calcination temperature is less than 650° C., the diffusion oflithium into the nickel composite oxide is not sufficient, and surpluslithium and unreacted nickel composite oxide remains, or the crystalstructure is not sufficiently uniform, and thus when used in a battery,sufficient battery characteristics are not obtained. Moreover, when thecalcination temperature is greater than 1000° C., intense sinteringoccurs between particles of the lithium nickel composite oxide, andabnormal particle growth occurs, so the particles become coarse and itis not possible to maintain a state of spherical secondary particles. Ineither case, not only is there a drop in battery capacity, the value ofthe cathode resistance also becomes high.

In the general expression described above, when the value “x” thatindicates the nickel content is 0.7 or less, from the aspect of causinglithium to sufficiently diffuse into the nickel composite oxide, thecalcination temperature is preferably 800° C. to 980° C., and morepreferably 850° C. to 950° C. On the other hand, when “x” is greaterthan 0.7, cationic mixing (migration of nickel into the lithium layerbecomes severe) occurs, so from the aspect of preventing a decrease inbattery capacity, the calcination temperature is preferably 650° C. to850° C., and more preferably 700° C. to 800° C.

(Calcination Time)

Of the calcination time, the hold time at a specified temperature ispreferably at least one hour or more, and more preferably 5 to 15 hours.When the hold time is less than one hour, there is a possibility thatlithium nickel composite oxide will not be generated sufficiently.

(Pre-Calcination)

Particularly, when lithium hydroxide or lithium carbonate is used as thelithium compound, before the calcination process, pre-calcination isperformed at a temperature lower than the calcination temperature suchas 350° C. to 800° C. or preferably 450° C. to 780° C., for a holdingtime of 1 to 10 hours, and preferably 3 to 6 hours. Alternatively, byslowing the speed of the rate of temperature increase until thetemperature reaches the calcination temperature, it is possible toessentially obtain the same effect as when pre-calcination is performed.In other words, performing pre-calcination at the reaction temperatureof lithium hydroxide or lithium carbonate and nickel composite oxide ispreferred. In this case, by maintaining the temperature at near thereaction temperature of lithium hydroxide and lithium carbonate,diffusion of the lithium into the heat-treated particles is performedsufficiently, and it is possible to obtain a uniform lithium nickelcomposite oxide.

(Calcination Atmosphere)

The calcination atmosphere is preferably an oxidizing atmosphere, so anatmosphere having an oxygen concentration of 10 volume % to 100 volume %is more preferred, and a mixed atmosphere of oxygen having the oxygenconcentration above and an inert gas is particularly preferred. In otherwords, calcination is preferably performed in an air atmosphere oroxygen current. When the oxygen concentration is less then 10 volume %,oxidation is not sufficient, so the crystallinity of the lithium nickelcomposite oxide may not be sufficient. Particularly, when the value “x”above is greater than 0.7, performing calcination in oxygen current iseven more preferred.

The furnace that is used in calcination is not particularly limited,however heating should be performed in an air atmosphere or oxygencurrent, and from the aspect of keeping the atmosphere in the furnaceuniform, an electric furnace in which there is no gas generation ispreferred, and a batch type or continuous type of furnace is used.

(Cracking)

The lithium nickel composite oxide that is obtained through calcinationmay undergo clumping or light sintering. In that case, cracking can beperformed, and as a result, it is possible to obtain lithium nickelcomposite oxide, or in other words, the cathode active material of thepresent invention. Cracking is an operation of breaking up a clump byapplying mechanical energy to plural secondary particles, which haveclumped together due to sintering necking or the like that occursbetween secondary particles during calcination, and separating thesecondary particles without destroying the secondary particlesthemselves.

(3) Nonaqueous-Electrolyte Secondary Battery

The nonaqueous-electrolyte secondary battery of the present inventionincludes a cathode, an anode and a nonaqueous electrolyte, and iscomposed of the same components as a typical nonaqueous-electrolytesecondary battery. The embodiments explained below are only examples,and the nonaqueous-electrolyte secondary battery of the presentinvention can also be applied to various modifications and improvementsbased on the embodiments disclosed in this specification.

3.1. Cathode

The cathode of a nonaqueous-electrolyte secondary battery ismanufactured such as described below using the cathode active materialfor a nonaqueous-electrolyte secondary battery that was obtainedaccording to the present invention.

First, a conductive material and binding agent are mixed with the powdercathode active material that was obtained according to the presentinvention, and as necessary, activated carbon or a solvent forcontrolling viscosity or the like is added, after which all of these aremixed to manufacture a mixed cathode paste. When doing this, therespective mixture ratios in the mixed cathode paste are also importantelements for setting the performance of the nonaqueous-electrolytesecondary battery. Taking the solid content of the mixed cathodematerial except the solvent to be 100 parts by weight, as in the cathodeof a typical nonaqueous-electrolyte secondary battery, preferably thecontent of the cathode active material is taken to be 60 to 95 parts byweight, the content of conductive material is taken to be 1 to 20 partsby weight and the content of the binding agent is taken to be 1 to 20parts by weight.

The obtained mixed cathode paste is applied, for example, to the surfaceof a collector made of aluminum foil, and then dried to release thesolvent. As necessary, pressure is applied using a roll press in orderto increase the electrode density. In this way, it is possible tomanufacture a sheet shaped cathode. A sheet shaped cathode can be cut toan appropriate size according to the intended battery, and used in themanufacture of the battery. However, the method for manufacturing thecathode is not limited to this example, and other methods could also beused.

As the conductive material, it is possible to use, for example, graphite(natural graphite, synthetic graphite, expanded graphite or the like),or a carbon black type material such as acetylene black, ketjen black orthe like.

The binding agent serves the purpose of binding together particles ofactive material, and, for example, it is possible to use polyvinylidenefluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber, ethylenepropylene diene rubber, styrene-butadiene, cellulose resin andpolyacrylic acid.

Moreover, as necessary, it is possible to add a solvent for dispersingthe active cathode material, conductive material and activated carbonand for dissolving the binding agent to the mixed cathode material. Morespecifically, it is possible to use an organic solvent such asN-methyl-2-pyrrolidone as the solvent. It is also possible to addactivated carbon to the mixed cathode material in order to increase theelectric double layer capacity.

3.2. Anode

An anode that is formed by applying a paste-like mixed anode material,which is formed by mixing a binding agent with metal lithium, lithiumalloy or other anode active material that is capable of occlusion anddesorption of lithium ions, and adding a suitable solvent, to thesurface of a collector made of a metal foil such as copper foil, thendrying and applying pressure as necessary to increase the electrodedensity can be used.

As the anode active material, it is possible, for example, to use anorganic calcined compound such as natural graphite, synthetic graphite,phenol resin and the like, or a powdered carbon substance such as cokeand the like. In this case, as the anode binding agent, as in the caseof the cathode, it is possible to use a fluorine containing resin suchas PVDF, and as a solvent for dispersing the active material and thebinding agent, it is possible to use an organic solvent such asN-methyl-2-pyrrolidone.

3.3. Separator

A separator is placed between the cathode and anode. The separatorseparates the cathode and anode and holds the electrolyte, and as theseparator it is possible to use a thin film made of polyethylene,polypropylene or the like, and that has many minute holes.

3.4. Nonaqueous Electrolyte

The nonaqueous electrolyte is an organic solvent in which lithium salthas been dissolved as a supporting electrolyte.

As the organic solvent it is possible to use one kind alone or a mixtureof two kinds or more of material selected from among a cyclic carbonatesuch as ethylene carbonate, propylene carbonate, butylene carbonate,trifluoro propylene carbonate and the like; a chain-shaped carbonatesuch as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate,dipropyl carbonate and the like; an ether compound such astetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane and the like;a sulfur compound such as ethyl methyl sulfone, butane sultone and thelike; and a phosphorus compound such as triethyl phosphate, trioctylphosphate and the like.

As the supporting electrolyte it is possible to use LiPF₆, LiBF₄,LiClO₄, LiAsF₆, LiN(CF₃SO₂)₂, a composite thereof, and the like.

Furthermore, the nonaqueous electrolyte can also include a radicalscavenger, a surfactant, a flame retardant and the like.

3.5. Shape and Construction of a Battery

A nonaqueous-electrolyte secondary battery of the present invention thatis constructed using the cathode, anode, separator and nonaqueouselectrolyte explained above can have various shapes, such as acylindrical shape or layered shape.

In the case of any shape, the cathode and anode are layered by way of aseparator to form an electrode assembly, nonaqueous electrolyte isimpregnated into the obtained electrode assembly, a cathode collectorand a cathode terminal that passes to the outside, an anode collectorand an anode terminal that passes to the outside are connected bycollector leads, and this is all sealed in a battery case to completelyform a nonaqueous-electrolyte secondary battery.

3.6. Characteristics

The nonaqueous-electrolyte secondary battery of the present inventionhas a high initial discharge capacity of 150 mAh/g or more, a lowcathode resistance of 10Ω or less, and is a high capacity and highoutput battery. Moreover, when the cathode active material is comparedwith that of a conventional lithium cobalt oxide or lithium nickeloxide, the battery is superior in regards to high thermal stability andsafety.

3.7. Application

The nonaqueous-electrolyte secondary battery of the present invention issuitable as a power source for compact portable electronic devices(notebook personal computer, portable telephone, and the like) thatusually require a high capacity power source.

The secondary battery of the present invention is also suitable as apower source for a battery used as the power source for a motor drivethat requires high output. As the size of a battery increases,maintaining safety becomes more difficult, and expensive protectivecircuits become indispensable. However, the nonaqueous-electrolytesecondary battery of the present invention has excellent safety withoutan increase in the battery size, so not only is maintaining safety easy,the expensive protective circuits can be simplified, and the cost can bedecreased. Furthermore, compact size and high output are possible, sothe secondary battery is suitable as a power source for transportequipment in which installation space is limited.

EXAMPLES

In the following, the present invention will be explained in detail withreference to some examples and comparative examples. In all of theexamples and comparative examples, special grade chemical specimensmanufactured by Wako Pure Chemical Industries Co., Ltd. were used in themanufacture of the composite hydroxide, cathode active material andsecondary battery.

Example 1

[Manufacturing of Nickel Composite Hydroxide]

(Nucleation Process)

First, 7.2 L of water is put into a 50 L reaction tank with a baffleboard that is capable of maintaining the atmosphere in the tank, andwhile mixing at 500 rpm using inclined paddle type impellers, the oxygenconcentration of the reaction tank atmosphere was decreased to 1 volume% or less by passing nitrogen gas through the tank, and the tanktemperature was adjusted until the temperature became 40° C. To thisreaction tank, proper amounts of 25 weight % of sodium hydroxide aqueoussolution and 25 weight % of ammonia water were added, and at a standardsolution temperature of 25° C., the pH value of the reaction solution inthe tank was adjusted to 12.6, and the ammonia concentration wasadjusted to 10 g/L to obtain a pre-reaction aqueous solution.

Next, nickel sulfate and manganese sulfate (metal element mole ratio,Ni:Mn=50:50) were dissolved in water, then 35 ml of the obtained 1.9mol/L mixed aqueous solution was added, and with ammonia concentrationin the reaction aqueous solution (nucleation aqueous solution)maintained at the value above, crystallization (nucleation) wasperformed while adding 25% sodium hydroxide aqueous solution so that thepH value was maintained at 12.6 (nucleation pH).

(Particle Growth Process)

After nucleation was complete, 32 weight % sulfuric acid was added untilthe pH value at a standard solution temperature of 25° C. became 11.6(nuclei growth pH). After the pH value of the reaction aqueous solutionreached 11.6, a fixed amount of 25 weight % ammonia water was added tothe reaction aqueous solution (particle growth aqueous solution) inorder to maintain the ammonia concentration at the value above, and 25weight % sodium hydroxide aqueous solution was added to control the pHvalue at 11.6, and in this state, the mixed aqueous solution was addedat 103.2 ml/min, and by keeping the atmosphere at the value above,crystallization was continued for 4 hours. After that, crystallizationwas stopped, and the solution was allowed to rest to promoteprecipitation of the product, after which crystallization was ended. Theproduct was then washed in water, filtered and dried.

In the crystallization above, the pH was controlled by adjusting thesupply flow rate of sodium hydroxide aqueous solution using a pHcontroller, and the fluctuation range was within the range of ±0.2 ofthe set value. Moreover, the agitation power requirement per unit volumeof the reaction solution was estimated from the rotation torque androtation speed to be 1.3 kW/m³ to 2.2 kW/m³.

[Analysis of the Composite Hydroxide]

A sample of the obtained composite hydroxide was dissolved using aninorganic acid, after which chemical analysis was performed using theICP emission spectrography, and the composition was found to beNi_(0.50)Mn_(0.50)(OH)_(2+a) (0≤a≤0.5).

Moreover, for this composite hydroxide, the average particle size andthe value of the index [(d90−d10)/average particle size] that indicatesthe particle size distribution were calculated and found from the volumeintegration value that was measured using a laser diffraction-scatteringtype particle size distribution measuring device (Microtrac HRA,manufactured by Nikkiso Co., Ltd.). As a result, it was found that theaverage particle size was 9.1 μm, and the index [(d90−d10)/averageparticle size] was 0.53.

Next, SEM (scanning electron microscope S-4700, HitachiHigh-Technologies Corporation) observation (magnification rate: 5000×)of the obtained composite hydroxide was performed, and it was found thatthe composite hydroxide had a nearly spherical shape, and the particlesize was nearly uniform. The results of the SEM observation areillustrated in FIG. 5.

Moreover, a sample of the obtained composite hydroxide was embedded inresin, and cross-section polishing was performed, after which SEMobservation at a magnification rate of 5000× was performed, and as aresult it was found that the composite hydroxide was composed ofsecondary particles, and those secondary particles were composed ofneedle shaped and plate shaped primary particles (the particle size wasabout 0.8 μm). The cross-section SEM observation results are illustratedin FIG. 6.

The characteristics of the composite hydroxide obtained in this exampleare illustrated in Table 1. The same contents for examples 2 to 5 andcomparative examples 1 to 5 are also illustrated in Table 1.

[Manufacture of the Cathode Active Material]

The composite hydroxide described above was heat treated in an air flow(oxygen: 21 volume %) for 6 hours at 700° C., and recovered asheat-treated particles.

Lithium carbonate was weighed so that Li/Me=1.20, then sufficientlymixed with the heat-treated particles above using a shaker mixer(TURBULA Type T2C, Willy A. Bachofen AG) to obtain a lithium mixture.This mixture was then pre-calcined in an air flow (oxygen: 21 volume %)for 4 hours at 500° C., calcined for 10 hours at 900° C. and thencooled, after which the mixture was further cracked to obtain a cathodeactive material for a nonaqueous-electrolyte secondary battery.

[Analysis of the Cathode Active Material]

The obtained cathode active material was chemically analyzed by the samemethod as used for the composite hydroxide, and the composition wasfound to be Li_(1.20)Ni_(0.50)Mn_(0.50)O₂. Using the same method as usedfor the composite hydroxide, the particle size distribution of theobtained cathode active material was measured, and the average particlesize was 9.2 μm, and the index [(d90−d10)/average particle size] was0.55.

Moreover, using the same method as used for the composite hydroxide, SEMobservation (magnification rate: 5000×) and cross-section SEMobservation (magnification rate: 5000×) of the cathode active materialwas performed, and the obtained cathode active material was found to benearly spherical, and the particle size was mostly uniform. The resultsof the SEM observation for this cathode active material are illustratedin FIG. 7. On the other hand, in the cross-section SEM observation, itwas found that the cathode active material had a solid structure ofsintered primary particles. The results of the cross-section SEMobservation of this cathode active material are illustrated in FIG. 8.

Furthermore, the specific surface area was measured using a flow typegas adsorption specific surface area measurement device (Multisorb,Yuasa Ionics Co., Ltd.) and found to be 0.6 m²/g. The obtained cathodeactive material was also analyzed by powder X-ray diffraction by Cu-Kαrays using an X-ray diffraction device (X'Pert PRO, PANalytical B.V.),and it was found that the crystal structure of the cathode activematerial was hexagonal layered crystal lithium nickel manganesecomposite oxide single phase. It was also found from cross-section SEMobservation that the structure was a solid structure.

[Manufacture of Secondary Battery]

For evaluating the obtained cathode active material for anonaqueous-electrolyte secondary battery, a battery as described belowwas manufactured. First, 52.5 mg of the cathode active material for anonaqueous-electrolyte secondary battery, 15 mg of acetylene black and7.5 mg of polytetra ethylene fluoride resin (PTFE) were mixed, and apressure of 100 MPa was applied to press form a cathode (electrode forevaluation) (1) having a 11 mm diameter and 100 μm thickness asillustrated in FIG. 14. The formed cathode (1) was then dried for 12hours at 120° C. in a vacuum drier. This cathode (1) was then used toform a 2032 type coin battery (B) such as illustrated in FIG. 14 insidea glove box that was in an Ar atmosphere that was managed at a dew pointof ˜80° C. Lithium metal having a diameter of 17 mm and a thickness of 1mm was used as the anode (2), and 1M of a mixed solution of equal partsof ethylene carbonate (EC) and diethyl carbonate (DEC) (Tomiyama PureChemical Industries, Ltd.) with LiClO₄ as a supporting electrolyte wasused as the electrolyte. A porous polyethylene film having a filmthickness of 25 μm was used as the separator (3). Moreover, the coinbattery (B) had a gasket (4), and was assembled into a coin shapedbattery with a cathode can (5) and anode can (6).

[Battery Evaluation]

The initial electric discharge capacity, the cycle capacity maintenancerate, and the cathode resistance that are used to evaluate theperformance of the obtained battery (B) are defined below.

The initial electric discharge capacity is the electric dischargecapacity when, after the coin battery (B) has been allowed to sit for 24hours after assembly and the open circuit voltage (OCV) has stabilized,the battery has been charged until it reaches the cutoff voltage 4.3 Vwith a current density with respect to the cathode of 0.1 mA/cm², andthen after a 1 hour rest, is allowed to discharge to a cutoff voltage of3.0 V. A multi-channel voltage/current generator (R6741A, AdvantestCorporation) was used for measuring the charge/discharge capacity.

The cathode resistance is the resistance value that is measured by thealternating current impedance method using a coin battery (B) that hasbeen charged to a charging potential of 4.1 V. When the resistance wasmeasured by the alternating current impedance method using a frequencyresponse analyzer and a potentiostat/galvanostat (Solatron), a Nyquistplot such as illustrated in FIG. 13 was obtained. The plot is expressedas a sum of characteristic curves that illustrate the solutionresistance, the anode resistance and capacity, and the cathoderesistance and capacity, so a fitting calculation was performed using anequivalent circuit, and the value of the cathode resistance wasmeasured.

A coin type battery having a cathode that was formed using the cathodeactive material above was evaluated, and it was found that the initialelectric discharge capacity was 207.6 mAh/g, and the cathode resistancewas 8.5Ω.

The characteristics of the cathode active material that was obtained inthis example, and the evaluations of a coin type battery that wasmanufactured using the cathode active material are illustrated in Table2. The same contents for examples 2 to 5 and comparative examples 1 to 5below are also illustrated in Table 2.

Example 2

Except for forming a mixed aqueous solution by dissolving sodiumtungstate in water in addition to nickel sulfate and manganese sulfatein the process for manufacturing a composite hydroxide, a cathode activematerial for a nonaqueous-electrolyte secondary battery was obtained andevaluated in the same way as in example 1. In this mixed aqueoussolution, the element molar ratios of the metals were adjusted so thatNi:Mn:W=49.75:49.75:0.5. The composition of the obtained compositehydroxide was Ni_(0.4975)Mn_(0.4975)W_(0.005)(OH)_(2−a) (0≤a≤0.5).Moreover, the composition of the obtained cathode active material wasLi_(1.20)Ni_(0.4975)Mn_(0.4975)W_(0.005)O₂, and from powder X-raydiffraction, it was found that the cathode active material was composedof hexagonal crystals of layered lithium nickel manganese compositeoxide single phase.

Example 3

Except for forming a mixed aqueous solution by dissolving zirconiumsulfate in water in addition to nickel sulfate and manganese sulfate inthe process for manufacturing a composite hydroxide, a cathode activematerial for a nonaqueous-electrolyte secondary battery was obtained andevaluated in the same way as in example 1. In this mixed aqueoussolution, the element molar ratios of the metals were adjusted so thatNi:Mn:Zr=49.75:49.75:0.5. The composition of the obtained compositehydroxide was Ni_(0.4975)Mn_(0.4975)Zr_(0.005)(OH)_(2+a) (0≤a≤0.5).Moreover, the composition of the obtained cathode active material wasLi_(1.20)Ni_(0.4975)Mn_(0.4975)Zr_(0.005)O₂, and from powder X-raydiffraction, it was found that the cathode active material was composedof hexagonal crystals of layered lithium nickel manganese compositeoxide single phase.

Example 4

Except for making the ammonia concentration 15 g/L, performing theparticle growth process for 4 hours and then stopping agitating to allowthe solid content to precipitate out, removing the supernatant liquiduntil the amount was the same as the amount of liquid after seedcrystallization, and then performing the particle growth process for 4hours in the process for manufacturing composite hydroxide, a cathodeactive material for a nonaqueous-electrolyte secondary battery wasobtained and evaluated in the same way as in example 1. The compositionsof the obtained composite hydroxide and cathode active material were thesame as that in example 1, and it was found by powder X-ray diffractionthat the cathode active material was composed of hexagonal crystals oflayered lithium nickel manganese composite oxide single phase.

Example 5

Except for rotating the agitating blades at 600 rpm, and the agitationpower requirement per unit volume of the reaction aqueous solution inthe nucleation process and particle growth process being adjusted to be2.9 to 4.0 kW/m³, a cathode active material for a nonaqueous-electrolytesecondary battery was obtained and evaluated in the same way as inexample 1. The compositions of the obtained composite hydroxide andcathode active material were the same as that in example 1, and it wasfound by powder X-ray diffraction that the cathode active material wascomposed of hexagonal crystals of layered lithium nickel manganesecomposite oxide single phase.

Comparative Example 1

Except that the pH value during nucleation and particle growth wasmaintained at a fixed value of 11.6 at a standard solution temperatureof 25° C., a cathode active material for a nonaqueous-electrolytesecondary battery was obtained and evaluated in the same way as inexample 1. The compositions of the obtained composite hydroxide andcathode active material were the same as that in example 1, and it wasfound by powder X-ray diffraction that the cathode active material wascomposed of hexagonal crystals of layered lithium nickel manganesecomposite oxide single phase.

Comparative Example 2

Except that the pH value during nucleation and particle growth wasmaintained at a fixed value of 12.6 at a standard solution temperatureof 25° C., a nickel manganese composite hydroxide was obtained in thesame way as in example 1. However, new nuclei were generated during theentire crystallization period, so irregular shaped particles having awide particle size distribution and including gel type precipitate wereobtained, and solid-liquid separation was difficult, so processing wasterminated.

Comparative Example 3

Except that the calcination temperature was 1050° C., a cathode activematerial for a nonaqueous-electrolyte secondary battery was obtained andevaluated in the same way as in example 1. The compositions of theobtained composite hydroxide and cathode active material were the sameas that in example 1. However, from the results of X-ray diffractionmeasurement, the hexagonal crystal structure was lost, and performanceas a cathode active material could not be expected, so batteryevaluation was not performed.

Comparative Example 4

Except that the agitating blades were rotated at 200 rpm, and theagitation power requirement per unit volume of the reaction aqueoussolution in the nucleation process and particle growth process wasadjusted to be 2.9 kW/m³ to 4.0 kW/m³, a composite hydroxide wasobtained and evaluated in the same way as in example 1. The compositionsof the obtained composite hydroxide and cathode active material wereNi_(0.5)Mn_(0.5)(OH)_(2+a) (0≤a≤0.5) and Li_(1.20)Ni_(0.5)Mn_(0.5)O₂,respectively, and the index [(d90−d10)/average particle size] was 1.14.The particle size distribution of the composite hydroxide was large, sowas a cathode active material for a nonaqueous-electrolyte secondarybattery was not formed.

Comparative Example 5

Except for the agitating blades being turbine blades, and being rotatedat 1000 rpm so that the agitation power requirement per unit volume ofreaction aqueous solution in the nucleation process and particle growthprocess became 4.5 kW/m³ to 6.0 kW/m³, a cathode active material for anonaqueous-electrolyte secondary battery was obtained and evaluated inthe same way as in example 1. The compositions of the obtained compositehydroxide and cathode active material were the same as that in example1, however, the average particle size remained at 5.2 μm. It was foundby powder X-ray diffraction that the cathode active material wascomposed of hexagonal crystals of layered lithium nickel manganesecomposite oxide single phase.

TABLE 1 Agitation Average (d90 − d10)/ Oxygen Tank NH₃ pH power particleAverage Additional concentration temperature concentration NucleationParticle fluctuation requirement size particle elements (volume %) (°C.) (g/L) pH growth pH width (kW/m³) (μm) size Example 1 — 1 or less 4010 12.6 11.6 0.2 1.3-2.2 9.1 0.53 Example 2 W 1 or less 40 10 12.6 11.60.2 1.3-2.2 9.4 0.52 Example 3 Zr 1 or less 40 10 12.6 11.6 0.2 1.3-2.210.3 0.54 Example 4 — 1 or less 40 15 12.6 11.6 0.2 1.3-2.2 11.1 0.55Example 5 — 1 or less 40 10 12.6 11.6 0.2 2.9-4.0 9.1 0.53 CX-1 — 1 orless 40 10 11.6 11.6 0.2 1.3-2.2 15.3 0.53 CX-2 — 1 or less 40 10 12.612.6 0.2 1.3-2.2 — — CX-3 — 1 or less 40 10 12.6 11.6 0.2 1.3-2.2 9.10.53 CX-4 — 1 or less 40 10 12.6 11.6 0.2 0.2-0.4 10.1 1.14 CX-5 — 1 orless 40 10 12.6 11.6 0.2 4.5-6.0 5.2 0.50 (CX = Comparative Example)

TABLE 2 Average (d90 − d10)/ Specific Initial electric Heat Pre-particle Average surface Tap discharge treatment calcination Calcinationsize particle area density capacity Resistance ° C. Time ° C. Time ° C.Time (μm) size (m²/g) (g/m³) Structure (mAh/g) (Ω) Example 1 700 6 500 4900 10 9.2 0.55 0.6 2.2 Solid 207.6 8.5 Example 2 700 6 500 4 900 10 9.00.53 0.6 2.1 Solid 205.8 7.1 Example 3 700 6 500 4 900 10 9.2 0.51 0.62.1 Solid 206.8 8.1 Example 4 700 6 500 4 900 10 9.7 0.55 0.6 2.2 Solid205.8 8.2 Example 5 700 6 500 4 900 10 9.3 0.54 0.6 2.1 Solid 206.1 8.0CX-1 700 6 500 4 900 10 15.1  0.78 0.5 2.2 Solid 206.0 18.4  CX-2 — — —— — — — — — — — — — CX-3 700 6 500 4 1050  10 18.6  0.87 — — — — — CX-4— — — — — — — — — — — — — CX-5 700 6 500 4 900 10 5.3 0.52 1.2 2.0 Solid199.8 8.1 (CX = Comparative Example)[Evaluation]

The composite hydroxide and the cathode active material of examples 1 to5 were manufactured according to the present invention, so the averageparticle size and the value [(d90−d10)/average particle size], which isan index that indicates the expanse of the particle size distribution,were within the preferable ranges for all, and the particles had goodparticle size distribution and nearly uniform particle size. Coinbatteries that were made using the cathode active material of theseexamples had high initial electric discharge capacity, and low cathoderesistance, and had excellent battery characteristics.

In comparative example 1, the pH values during nucleation and particlegrowth were both 12 or less, so the amount of nucleation wasinsufficient, and both the composite hydroxide and cathode activematerial had a large particle size. Therefore, a coin battery that usedthis cathode active material had insufficient reaction surface area, andthe cathode resistance was higher than in the examples.

In comparative example 2, the pH values during nucleation and particlegrowth were both 12 or less, so new nuclei were generated during theenter period of the crystallization reaction, and particles became smalland clumped together, so the particle size distribution became large,and manufacturing the cathode active material became difficult.

In comparative example 3, the manufacturing process for the cathodeactive material was not according to the present invention, so it wasimpossible to obtain a cathode active material having goodcharacteristics.

In comparative example 4 and comparative example 5, the agitatingconditions for the reaction aqueous solution were not according to thepresent invention, so in comparative example 4, the particle sizedistribution was outside of the range of the present invention, and incomparative example 5, the average particle size of the compositehydroxide particles did not reach 7 μm, and the average particle size ofthe cathode active material did not reach 8 μm.

From the results above, it can be seen that by manufacturing a nickelmanganese composite hydroxide and cathode active material using themanufacturing method of the present invention, a nonaqueous-electrolytesecondary battery that uses the cathode active material has a highinitial electric discharge capacity and low cathode resistance, and is abattery having excellent battery characteristics.

Example 6

[Manufacture of Nickel Composite Hydroxide]

Composite hydroxide was manufactured as described below.

(Nucleation Process)

Except for using 2.2 mol/L of aqueous solution obtained by dissolvingnickel sulfate, manganese sulfate and cobalt sulfate (metal elementmolar ratios; Ni:Mn:Co=50:25:25) in water as a mixed aqueous solutionand adding 35 ml of this mixed aqueous solution to the reaction aqueoussolution, crystallization (nucleation) was performed in the same way asin example 1.

(Particle Growth Process)

Crystallization (particle growth) was performed in the same way as inexample 1. In this crystallization process, the pH fluctuation width waswithin the range of ±0.2 of the set value. Moreover, the agitation powerrequirement per unit volume of the reaction aqueous solution wasestimated from the rotation torque and rotation speed to be 1.3 to 3.2kW/m³.

[Analysis of the Composite Hydroxide]

After a sample of the obtained composite hydroxide was dissolved usinginorganic acid, chemical analysis was performed using the ICP emissionspectrography, and the composition was found to beNi_(0.50)Mn_(0.25)Co_(0.25)(OH)_(2+a) (0≤a≤0.5). The average particlesize was 9.4 μm, and the index [(d90−d10)/average particle size] was0.51.

The characteristics of the composite hydroxide that was obtained in thisexample are illustrated in Table 3. The same contents for examples 7 and8 and comparative examples 6 and 7 are also illustrated in Table 3.

[Manufacture of the Cathode Active Material]

Except for heat treating the composite hydroxide described above in anair flow (oxygen: 21 volume %) for 12 hours at 150° C. and recovering asheat-treated particles, weighing the lithium carbonate so thatLi/Me=1.15, mixing, and then pre-calcining in an air flow (oxygen: 21volume %) for 4 hours at 760° C., and calcining for 10 hours at 860° C.,a cathode active material for a nonaqueous-electrolyte secondary batterywas obtained in the same way as in example 1.

[Analysis of the Cathode Active Material]

The obtained cathode active material was chemically analyzed by the samemethod as used for the composite hydroxide, and the composition wasfound to be Li_(1.20)Ni_(0.50)Mn_(0.25)Co_(0.25)O₂. From powder X-raydiffraction, it was found that this cathode active material washexagonal layered crystal lithium nickel manganese composite oxidesingle phase, and from cross-section SEM observation it was found thatthe structure was a solid structure.

The obtained composite hydroxide and cathode active material wereevaluated in the same way as in example 1, and the characteristics ofthe obtained cathode active material, and evaluations of coin typebatteries that were manufactured using this cathode active material areillustrated in Table 4. The same contents for examples 6 and 7 andcomparative examples 4 and 5 are also illustrated in Table 4.

Example 7

Except for making the agitating speed during the nucleation process andgrowth process 400 rpm, and increasing the rotating speed 200 rpm at atime every 20 minutes up until 60 minutes after the growth process, acathode active material was obtained and evaluated in the same way as inexample 6. The compositions of the obtained composite hydroxide andcathode active material were the same as in example 6, and from powderX-ray diffraction, it was found that the cathode active material washexagonal layered crystal lithium nickel manganese composite oxidesingle phase.

The agitation power requirement per unit volume of the reaction aqueoussolution was estimated from the rotation torque and rotation speed to be0.7 to 3.6 kW/m³.

Example 8

Except for forming a mixed aqueous solution by dissolving nickelsulfate, cobalt sulfate and aluminum sulfate (metal element molar ratio;Ni:Co:Al=82:15:3) in water in the process for manufacturing compositehydroxide, then heat treating the obtained composite hydroxide in an airflow (oxygen: 21 volume %) for 6 hours at 700° C. and recovering asheat-treated particles, obtaining a lithium mixture by mixing theheat-treated particles with lithium hydroxide so that Li/Me=1.02,pre-calcining this mixture in an oxygen air flow for 4 hours at 500° C.,and calcining for 24 hours at 730° C., a cathode active material for anonaqueous-electrolyte secondary battery was obtained in the same was asin example 6. The composition of the obtained composite hydroxide wasNi_(0.82)Co_(0.15)Al_(0.03)(OH)_(2+a) (0≤a≤0.5). Moreover, thecomposition of the cathode active material that was obtained from thiscomposite hydroxide was Li_(1.02)Ni_(0.82)Mn_(0.15)Al_(0.03)O₂, and frompowder X-ray diffraction, it was found that the cathode active materialwas hexagonal layered crystal lithium nickel composite oxide singlephase.

Comparative Example 6

Except for adjusting the flow rate of nitrogen gas in the reaction tank,and making the oxygen concentration of the atmosphere in the reactiontank 2.0 volume % during crystallization, cathode active material wasobtained and evaluated in the same way as in example 6. The compositionsof the obtained composite hydroxide and cathode active material were thesame as in example 6, and from powder X-ray diffraction, it was foundthat the cathode active material was hexagonal layered crystal lithiumnickel manganese composite oxide single phase.

Comparative Example 7

A reaction tank having a overflow pipe at the top was used forcontinuous crystallization, and in an air atmosphere, the pH value ofthe reaction aqueous solution was kept at a fixed value of 11.0 at astandard solution temperature of 25° C., the same mixed aqueous solutionas in example 6, ammonia aqueous solution and sodium hydroxide solutionwere continuously added at a constant flow rate, and the overflowingslurry was continuously collected and analyzed using a typical method.The mean residence time in the reaction tank was 10 hours, and after theinside of the reaction tank reached an equilibrium state, the slurry wascollected and solid-liquid separation was performed to obtaincrystallized material; other than this, a cathode active material for anonaqueous-electrolyte secondary battery was obtained and analyzed inthe same way as in example 6. The composition of the obtained compositehydroxide and cathode active material was the same as in example 6, andfrom powder X-ray diffraction, it was found that the cathode activematerial was hexagonal layered crystal lithium nickel manganesecomposite oxide single phase.

TABLE 3 Agitating Average (d90 − d10)/ Oxygen Tank NH₃ pH Power particleAverage Additional concentration temperature concentration NucleationParticle fluctuation Requirement size particle elements (volume %) (°C.) (g/L) pH growth pH width (kW/m³) (μm) size Example 6 — 1 or less 4010 12.6 11.6 0.2 1.3-2.2 9.4 0.51 Example 7 — 1 or less 40 10 12.6 11.60.2 0.7-3.6 11.6 0.52 Example 8 Al 1 or less 40 10 12.6 11.6 0.2 1.3-2.29.9 0.50 CX-6 — 2 40 10 12.6 11.6 0.2 1.3-2.2 5.8 0.46 CX-7 — 1 or less40 10 11 11 0.2 1.3-2.2 10.5 0.74 (CX = Comparative Example)

TABLE 4 Average (d90 − d10)/ Specific Initial electric Heat Pre-particle Average surface Tap discharge treatment calcination Calcinationsize particle area density capacity Resistance ° C. Time ° C. Time ° C.Time (μm) size (m²/g) (g/m³) Structure (mAh/g) (Ω) Example 6 150 12 7604 860 10 10.7 0.47 0.8 2.1 Solid 161.3 4.1 Example 7 150 12 760 4 860 1011.9 0.46 0.8 2.1 Solid 161.7 4.0 Example 8 700 6 500 4 730 24 10.5 0.490.9 2.2 Solid 198.6 4.0 CX-6 150 12 760 4 860 10 5.7 0.45 1.3 1.7 Solid159.1 3.5 CX-7 150 12 760 4 860 10 10.6 0.77 0.7 2.0 Solid 160.2 13.5(CX = Comparative Example)[Evaluation]

The composite hydroxide and cathode active material of example 6 to 8were manufactured according to the manufacturing method of the presentinvention, so the average particle size and the value [(d90−d10)/Averageparticle size], which is an index that indicates the expanse of theparticle size distribution, were within the preferable ranges for all,and the particles had good particle size distribution and nearly uniformparticle size. Coin batteries that were made using the cathode activematerial of these examples had high initial electric discharge capacity,and low cathode resistance, and had excellent battery characteristics.

In comparative example 6, by making the oxygen concentration of theatmosphere inside the reaction tank 2.0 volume %, the growth of primaryparticles during particle growth was insufficient, so the particles weresuch that the average particle size was small, the specific surface areawas large, the tap density was low and the filling capability of theactive material in the electrode was insufficient.

In comparative example 7, a continuous crystallization method was used,so separation of nucleation and particle growth was not possible, andthe particle growth time was not fixed, so the particle sizedistribution became large. Therefore, even though the coin type batteryhad a high initial electric discharge capacity, the cathode resistancewas high.

From the results above, it was found that by manufacturing nickelcomposite hydroxide and a cathode active material using themanufacturing method of the present invention, a nonaqueous-electrolytesecondary battery that uses the cathode active material has a highinitial electric discharge capacity and low cathode resistance, and is abattery having excellent battery characteristics.

Example 9

[Manufacture of Composite Hydroxide]

Composite hydroxide was manufactured as described below.

(Nucleation Process)

A reaction tank (34 L) was filled about half with water, and then whileagitating at 500 rpm using tilted paddle type agitating blades, thetemperature inside the tank was set at 40° C. The atmosphere inside thereaction tank during this time was an air atmosphere (oxygenconcentration: 21 volume %). Next, suitable amounts of 25 weight %sodium hydroxide aqueous solution and 25 weight % ammonia water wereadded to the water inside the reaction tank, and the pH value of thereaction solution inside the tank was adjusted to be 13.0 at a standardsolution temperature of 25° C. Furthermore, the ammonia concentrationinside the reaction solution was adjusted to 15 g/L to obtain apre-reaction aqueous solution.

Next, nickel sulfate and manganese sulfate (metal element molar ratio;Ni:Mn=50:50) were dissolved in water, and the obtained 2.0 mol/L ofmixed aqueous solution was added to the pre-reaction aqueous solution inthe reaction tank at a rate of 88 ml/min to obtain a reaction aqueoussolution. At the same time, 25 weight % ammonia water and 25 weight %sodium hydroxide aqueous solution were also added to this reactionaqueous solution at a fixed rate, and with the ammonia concentration inthe reaction aqueous solution (nucleation aqueous solution) maintainedat the value above, crystallization (nucleation) was performed for 15seconds while controlling the pH value at 13.0 (nucleation pH).

(Particle Growth Process)

After nucleation was completed, only the supply of 25 weight % sodiumhydroxide aqueous solution was stopped temporarily until the pH value ofthe reaction aqueous solution become 11.6 at a standard solutiontemperature of 25° C.

After the pH value of the reaction aqueous solution reached 11.6, thesupply of 25 weight % sodium hydroxide aqueous solution to the reactionaqueous solution (particle growth aqueous solution) was restarted, andwith the ammonia concentration maintained at the value above, and the pHvalue controlled at 11.6 at a standard solution temperature of 25° C.,crystallization was continued for 30 minutes, and particle growth wasperformed, after which the supply of solution was stopped, and nitrogengas was allowed to flow through the tank at a rate of 5 L/min until theoxygen concentration of the space inside the reaction tank became 0.2volume % or less. After that, the supply of solution was restarted, andcrystallization was performed until 2 hours from the start of growth.

When the inside of the reaction tank became full of solution,crystallization was stopped, and by stopping mixing and allowing thesolution to rest, precipitation of the product was promoted. After that,half of the supernatant fluid was removed from the reaction tank, andcrystallization was performed for 2 hours (total of 4 hours), afterwhich crystallization was ended.

The product was washed, filtered and dried to obtain compositehydroxide. Switching from an air atmosphere to a nitrogen atmosphere wasperformed at a point in time from the start of the particle growthprocess that is 12.5% the total time of the particle growth process.

In crystallization above, the pH value was controlled by adjusting thesupply flow rate of sodium hydroxide aqueous solution by a pHcontroller, and the fluctuation width was within the range of ±0.2 theset value.

[Analysis of the Composite Hydroxide]

A sample of the obtained composite hydroxide was dissolved usinginorganic acid, after which chemical analysis was performed by ICPemission spectrography, and the composition was found to beNi_(0.5)Mn_(0.5)(OH)_(2+a) (0≤a≤0.5).

Moreover, for this composite hydroxide, the average particle size andthe value of the index [(d90−d10)/average particle size] that indicatesthe particle size distribution were calculated and found from the volumeintegration value that was measured using a laser diffraction-scatteringtype particle size distribution measuring device (Microtrac HRA,manufactured by Nikkiso Co., Ltd.). As a result, it was found that theaverage particle size was 8.7 μm, and the index [(d90−d10)/averageparticle size] was 0.53.

Next, SEM (scanning electron microscope S-4700, HitachiHigh-Technologies Corporation) observation (magnification rate: 5000×)of the obtained composite hydroxide was performed, and it was found thatthe composite hydroxide had a nearly spherical shape, and the particlesize was nearly uniform. The results of the SEM observation areillustrated in FIG. 9.

Moreover, a sample of the obtained composite hydroxide was embedded inresin, and cross-section polishing was performed, after which SEMobservation at a magnification rate of 5000× was performed, and as aresult it was found that the composite hydroxide was composed ofsecondary particles, and those secondary particles had a center sectionwhich was composed of needle shaped and flake shaped primary particles(the particle size was about 0.3 μm) and an outer-shell section whichwas formed on the outside of the center section and was composed ofprimary particles that were larger than the minute primary particles.The cross-section SEM observation results are illustrated in FIG. 10.The ratio of the thickness of the outer shell section that was foundfrom SEM observation of this cross section with respect to the particlesize of the secondary particles was 12%.

The characteristics of the composite hydroxide obtained in this exampleare illustrated in Table 5. The same contents for examples 10 to 12 andcomparative examples 8 and 9 are also illustrated in Table 5.

[Manufacture of the Cathode Active Material]

The composite hydroxide described above was heat treated in an air flow(oxygen: 21 volume %) for 12 hours at 150° C., converted to compositeoxide and recovered.

Lithium hydroxide was weighed so that Li/Me=1.35, then the lithiumhydroxide was mixed with the composite oxide to form a lithium mixture.Mixing was performed using a shaker mixer (TURBULA Type T2C, Willy A.Bachofen AG).

The obtained lithium mixture was then pre-calcined in an air flow(oxygen: 21 volume %) for 4 hours at 500° C., calcined for 4 hours at900° C. and then cooled, after which the mixture was further cracked toobtain a cathode active material.

[Analysis of the Cathode Active Material]

The average particle size of the obtained cathode active material wasmeasured by the same method as used for the composite hydroxide, theaverage particle size was 9.0 μm, and the index [(d90−d10)/averageparticle size] was 0.56.

Moreover, using the same method as used for the composite hydroxide, SEMobservation (magnification rate: 5000×) and cross-section SEMobservation (magnification rate: 5000×) of the cathode active materialwere performed, and the obtained cathode active material was found to benearly spherical, and the particle size was mostly uniform. The resultsof the SEM observation for this cathode active material are illustratedin FIG. 11. On the other hand, in the cross-section SEM observation, itwas found that the cathode active material had a hollow structure havingan outer-shell section of sintered primary particles, with a hollowsection in the inside. The results of the cross-section SEM observationof this cathode active material are illustrated in FIG. 12. From thisobservation it was found that the ratio of the thickness of theouter-shell section of the cathode active material with respect to theparticle size of the cathode active material was 11%.

The specific surface area of the obtained cathode active material wasmeasured using a flow type gas adsorption specific surface areameasurement device (Multisorb, Yuasa Ionics) and found to be 1.2 m²/g.

This cathode active material was also analyzed by powder X-raydiffraction by Cu-Kα rays using an X-ray diffraction device (X'Pert PRO,PANalytical), and it was found that the crystal structure of the cathodeactive material was hexagonal layered crystal lithium nickel manganesecomposite oxide single phase.

Furthermore, from compositional analysis of the cathode active materialusing the ICP emission spectrography, the composition was found to beLi_(1.36)Ni_(0.50)Mn_(0.50)O₂. The obtained composite hydroxide andcathode active material were evaluated in the same way as in example 1,and the evaluations of a coin type battery that was manufactured usingthe cathode active material are illustrated in Table 6. The samecontents for examples 10 to 12 and comparative examples 8 and 9 beloware also illustrated in Table 6.

Example 10

Except for switching from an air atmosphere to a nitrogen atmosphere ata point in time from the start of the particle growth process that was6.25% the total time of the particle growth process, a cathode activematerial for a nonaqueous-electrolyte secondary battery was obtained andevaluated in the same was as in example 9. The compositions of theobtained composite hydroxide and cathode active material were the sameas in example 9, where the structure of the composite hydroxide, as inexample 9, had a center section of needle shaped minute primaryparticles (particle size of about 0.3 μm), and an outer-shell section onthe outside of the center section having plate shaped primary particlesthat were larger than the minute primary particles (particle size of 0.7μm).

Example 11

Except for switching from an air atmosphere to a nitrogen atmosphere ata point in time from the start of the particle growth process that was25% the total time of the particle growth process, a cathode activematerial for a nonaqueous-electrolyte secondary battery was obtained andevaluated in the same was as in example 9. The compositions of theobtained composite hydroxide and cathode active material were the sameas in example 9, where the structure of the composite hydroxide, as inexample 9, had a center section of needle shaped minute primaryparticles (particle size of about 0.3 μm), and an outer-shell section onthe outside of the center section having plate shaped primary particlesthat were larger than the minute primary particles (particle size of 0.5μm).

Example 12

Except for forming a mixed aqueous solution by adjusting the pH value ofthe pre-reaction aqueous solution to 12.8 at a standard solutiontemperature of 25° C., adjusting the ammonia concentration in thesolution to 10 g/L and dissolving nickel sulfate, cobalt sulfate,manganese sulfate and zirconium sulfate (metal element molar ratio;Ni:Co:Mn:Zr=33.2:33.1:33.3:0.5) in water; obtaining a compositehydroxide that was coated with ammonium tungstate salt by dispersing theobtained composite hydroxide in an ammonium tungstate solution to form aslurry such that the concentration becomes 150 g/L, and then spraydrying that slurry with a micro-mist drier (MDL-050M, Fujisaki ElectricCo., Ltd.) having a three-flow nozzle; obtaining a lithium mixture bymixing in lithium hydroxide so that Li/Me=1.15; and pre-calcining thismixture in an oxygen flow for 4 hours at 760° C., and then calcining themixture for 10 hours at 950° C., a cathode active material for anonaqueous-electrolyte secondary battery was obtained and evaluated inthe same way as in example 9.

The composition of the obtained composite hydroxide wasNi_(0.33)Co_(0.33)Mn_(0.33)Zr_(0.005)W_(0.005)(OH)_(2+a) (0≤a≤0.5).Moreover, it was found that the composition of the cathode activematerial that was obtained from this composite hydroxide wasLi_(1.15)Ni_(0.332)Co_(0.331)Mn_(0.332)Zr_(0.005)W_(0.005)O₂, and frompowder X-ray diffraction it was found that the cathode active materialwas hexagonal layered crystal lithium nickel manganese composite oxidesingle phase. Moreover, in EDX analysis in cross-section SEMobservation, it was found that there was much tungsten near the surfaceof the particles of active material.

Comparative Example 8

Except for making the agitating speed 1200 rpm, starting the flow ofnitrogen gas at 60 minutes from the start of the nucleation process, acathode active material was obtained and evaluated in the same way as inexample 9. The atmosphere of the reaction tank before the flow ofnitrogen gas was an air atmosphere (oxygen concentration of 21 volume%), and the oxygen concentration in the reaction tank after the flow ofnitrogen gas was 1 volume %. The agitation power requirement per unitvolume of reaction aqueous solution that was estimated from the rotationtorque and rotation speed was 10.4 kW/m³ to 13 kW/m³. Moreover, thecompositions of the obtained composite hydroxide and cathode activematerial were the same as in example 9, and from powder X-raydiffraction it was found that the cathode active material was hexagonallayered crystal lithium nickel manganese composite oxide single phase.

In comparative example 8, the rotation speed was increased, theparticles were such that the average particle size became small, thespecific surface area became large, the tap density was low, and thefilling capability into an electrode of the particles was insufficient.

Comparative Example 9

Except for making the calcination conditions 1050° C. and 10 hours, acomposite hydroxide and cathode active material were obtained in thesame way as in example 9. The compositions of the obtained compositehydroxide and cathode active material were the same as in example 9, andfrom powder X-ray diffraction it was found that the cathode activematerial was hexagonal layered crystal lithium nickel manganesecomposite oxide single phase.

In comparative example 9, the calcination temperature was high andsintering occurred, so the specific surface area was low and the cathoderesistance became high.

TABLE 5 Oxygen concentration Before After At Tank NH₃ Additionalswitching switching switching temperature concentration NucleationParticle elements (volume %) (volume %) (%) (° C.) (g/L) pH growth pHEX-9 — Air (21) 0.2 or less 12.5 40 15 13 11.6 EX-10 — Air (21) 0.2 orless 6.25 40 15 13 11.6 EX-11 — Air (21) 0.2 or less 25 40 15 13 11.6EX-12 Zr, W Air (21) 0.2 or less 12.5 40 10 12.8 11.6 CX-8 — Air (21)  1 or less 25 40 15 13 11.6 CX-9 — Air (21) 0.2 or less 12.5 40 15 1311.6 Plate Agitating Average (d90 − d10)/ Minute shaped Outer-shell pHpower particle Average primary primary section fluctuation requirementsize particle particles particles thickness width (kW/m³) (μm) size (μm)(μm) ratio (%) EX-9 0.2 1.3-2.2 8.7 0.53 0.3 0.6 12 EX-10 0.2 1.3-2.28.4 0.54 0.3 0.7 15 EX-11 0.2 1.3-2.2 9.0 0.55 0.3 0.5 10 EX-12 0.21.3-2.2 10.2 0.54 0.3 0.6 10 CX-8 0.2 10.4-13   5.1 0.51 0.3 0.6 10 CX-90.2 1.3-2.2 8.7 0.53 0.3 0.6 12 (EX = Example, CX = Comparative Example)

TABLE 6 Average (d90 − d10)/ Specific Outer-shell Initial electric HeatPre- particle Average surface Tap section discharge treatmentcalcination Calcination size particle area density thickness capacityResistance ° C. Time ° C. Time ° C. Time (μm) size (m²/g) (g/m³)Structure (%) (mAh/g) (Ω) EX-9 150 12 500 4 900 4 9.0 0.56 1.2 2.4Hollow 11 156.3 0.39 EX-10 150 12 500 4 900 4 8.6 0.55 1.1 2.2 Hollow 14155.1 0.37 EX-11 150 12 500 4 900 4 9.3 0.58 0.9 2.3 Hollow 9 156.5 0.41EX-12 150 12 760 4 950 10 10.6 0.55 1.0 2.4 Hollow 9 155.7 0.43 CX-8 15012 500 4 900 4 5.5 0.49 1.2 1.7 Hollow 9 149.8 0.42 CX-9 150 12 500 41050 10 6.3 0.65 0.8 1.9 Hollow — 138.7 0.61 (EX = Example, CX =Comparative Example)

INDUSTRIAL APPLICABILITY

The nonaqueous-electrolyte secondary battery of the present invention issuitable as a power source for compact portable electronic devices(notebook personal computer, portable telephone, and the like) thatusually require a high capacity power source.

Moreover, the secondary battery of the present invention has excellentsafety, and compact size and high output are possible, so is suitable asa power source for transport equipment in which installation space islimited.

EXPLANATION OF REFERENCE NUMBERS

-   1 Cathode-   2 Anode-   3 Separator-   4 Gasket-   5 Cathode can-   6 Anode can-   B Coin battery

What is claimed is:
 1. A method for manufacturing a nickel compositehydroxide that is a precursor to a cathode active material for anonaqueous-electrolyte secondary battery, the nickel composite hydroxidebeing obtained by a crystallization reaction and that is expressed by ageneral expression:Ni_(x)Mn_(y)Co_(z)M_(t)(OH)_(2+a), wherein x+y+z+t=1, 0.3≤x, 0≤y≤0.55,0≤z≤0.4, 0≤t≤0.1, 0≤a≤0.5, and M is one or more kind of additionalelement that is selected from among Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Taand W, the method comprising: a nucleation process that performsnucleation by controlling a nucleation aqueous solution that includes ametal compound that contains at least nickel and an ammonium ion donorso that a pH value at a standard solution temperature of 25° C. becomes12.0 to 14.0; and a particle growth process causes nuclei that wereformed in the nucleation process to grow by controlling a particlegrowth aqueous solution that contains the nuclei so that the pH value ata standard solution temperature of 25° C. becomes 10.5 to 12.0, and sothat the pH value during the particle growth process is lower than thepH value during the nucleation process; and the crystallization reactionbeing performed in a non-oxidizing atmosphere at least in a range afterthe processing time exceeds at least 40% of the total time of theparticle growth process from the start of the particle growth processwhere the oxygen concentration is 1 volume % or less, and withcontrolling an agitation power requirement per unit volume into a rangeof 0.5 kW/m³ to 4 kW/m³ at least during the nucleation process.
 2. Themanufacturing method for a nickel composite hydroxide according to claim1, wherein the non-oxidizing atmosphere is an inert gas atmosphere. 3.The manufacturing method for a nickel composite hydroxide according toclaim 1, wherein the particle growth aqueous solution is formed byadjusting the pH value of the nucleation aqueous solution after thenucleation process has finished.
 4. The manufacturing method for anickel composite hydroxide according to claim 1, wherein the particlegrowth aqueous solution is formed by adding a solution that includes thenuclei that were formed in the nucleation process to an aqueous solutionthat is different than the nucleation aqueous solution in which thenuclei were formed.
 5. The manufacturing method for a nickel compositehydroxide according to claim 1, wherein, in the particle growth process,part of the liquid of the particle growth aqueous solution is removed.6. The manufacturing method for a nickel composite hydroxide accordingto claim 1, wherein an ammonium concentration of the aqueous solutionsin the nucleation process and particle growth process is kept within therange of 3 g/L to 25 g/L.
 7. The manufacturing method for a nickelcomposite hydroxide according to claim 1, wherein the nickel compositehydroxide that was obtained in the particle growth process is covered bya compound that includes the one or more kind of the additionalelements.
 8. The manufacturing method for a nickel composite hydroxideaccording to claim 1, wherein the nickel composite hydroxide isconstructed by nearly spherical secondary particles that are formed byplate shaped and/or needle shaped plural primary particles clumpingtogether; the secondary particles having an average particle size thatis greater than 7 μm and less than or equal to 15 μm, and a value[(d90−d10)/average particle size], which is an index that indicates theextent of the particle size distribution, is 0.55 or less, wherein d90is the particle size in a point where cumulative volume is 90% of theentire volume when the particle size distribution of the secondaryparticles is measured from the first particle size side when the numberof particles of each particle size is similarly accumulated as theparticle size for d10, and that accumulated volume is 90% of the totalvolume of all particles.
 9. The manufacturing method for a nickelcomposite hydroxide according to claim 1, wherein, during the wholeprocess of the nucleation process and the particle growth process, thecrystallization reaction is performed in a non-oxidizing atmospherewhere the oxygen concentration is 1 volume % or less.
 10. Themanufacturing method for a nickel composite hydroxide according to claim9, wherein the nickel composite hydroxide is constructed by nearlyspherical secondary particles that are formed by plate shaped and/orneedle shaped plural primary particles clumping together; the secondaryparticles having an average particle size that is greater than 7 μm andless than or equal to 15 μm, and a value [(d90−d10)/average particlesize], which is an index that indicates the extent of the particle sizedistribution, is 0.55 or less, wherein d90 is the particle size in apoint where cumulative volume is 90% of the entire volume when theparticle size distribution of the secondary particles is measured fromthe first particle size side when the number of particles of eachparticle size is similarly accumulated as the particle size for d10, andthat accumulated volume is 90% of the total volume of all particles, andwherein the primary particles have an average particle size of 0.3 μm to3 μm.
 11. The manufacturing method for a nickel composite hydroxideaccording to claim 1, wherein the nickel content and the manganesecontent of the nickel composite hydroxide are regulated in the generalexpression so as to be 0.3≤x≤0.7 and 0.1≤y≤0.55, respectively, and thenucleation is performed in the nucleation process in an oxidizingatmosphere where the oxygen concentration is greater than 1 volume %,after which the atmosphere is switched from the oxidizing atmosphere tothe non-oxidizing atmosphere in which the oxygen concentration is 1volume % or less in a range of from 0% to 40% of the total time of theparticle growth process from the start of the particle growth process.12. The manufacturing method for a nickel composite hydroxide accordingto claim 11, wherein the oxygen concentration in the oxidizingatmosphere is 10 volume % or greater.
 13. The manufacturing method for anickel composite hydroxide according to claim 11, wherein the nickelcomposite hydroxide is constructed by nearly spherical secondaryparticles that are formed by plate shaped and/or needle shaped pluralprimary particles clumping together; the secondary particles having anaverage particle size that is greater than 7 μm and less than or equalto 15 μm, and a value [(d90−d10)/average particle size], which is anindex that indicates the extent of the particle size distribution, is0.55 or less, wherein d90 is the particle size in a point wherecumulative volume is 90% of the entire volume when the particle sizedistribution of the secondary particles is measured from the firstparticle size side when the number of particles of each particle size issimilarly accumulated as the particle size for d10, and that accumulatedvolume is 90% of the total volume of all particles, wherein thesecondary particles have a center section composed of minute primaryparticles, and an outer-shell section on the outside of the centersection composed of primary particles that are larger than the minuteprimary particles, and wherein the minute primary particles have anaverage particle size of 0.01 μm to 0.3 μm, and the primary particlesthat are larger than the minute primary particles have an averageparticle size of 0.3 μm to 3 μm.